EP2726582A1 - Schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern - Google Patents

Schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern

Info

Publication number
EP2726582A1
EP2726582A1 EP12731280.9A EP12731280A EP2726582A1 EP 2726582 A1 EP2726582 A1 EP 2726582A1 EP 12731280 A EP12731280 A EP 12731280A EP 2726582 A1 EP2726582 A1 EP 2726582A1
Authority
EP
European Patent Office
Prior art keywords
group
composition
additives
base stock
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12731280.9A
Other languages
English (en)
French (fr)
Inventor
Jacob J. Habeeb
Dominick N. Mazzone
Todd T. NADASDI
Douglas E. Deckman
Benjamin D. EIRICH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP2726582A1 publication Critical patent/EP2726582A1/de
Withdrawn legal-status Critical Current

Links

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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C10M2203/065—Well-defined aromatic compounds 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • 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
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C10M2209/1065—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/06—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
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present disclosure relates to lubricating compositions containing one or more polyalkylene glycol mono ethers and one or more additives, and methods for improving the performance properties of lubricating compositions with polyalkylene glycol mono ethers.
  • Lubricant fuel/energy efficiency will be an important feature for future automotive engine lubricants and commercial vehicle engine lubricants.
  • lower viscosity fluids e.g., belo about 15 cSt at 100°C.
  • Lower viscosity is known to impart lower viscous drag thus offering better energy efficiency or fuel economy.
  • improved antiwear properties and film thickness are beneficial for increasing the lifetime of engine components.
  • PAG fluids have been employed as lubricant base stocks.
  • PAG fluids possess performance advantages thai provide good efficiency, including very low friction/traction for energy efficiency and good lubricity (in hydrodynamic, mix, and boundary lubrication conditions).
  • PAG fluids also have other desirable properties, including high viscosity index (VI), low pour point, and excellent cleanliness.
  • VI high viscosity index
  • PAG fluids have numerous drawbacks, including lack of miscibility and compatibility with mineral and synthetic hydrocarbon-based lubricants. This has limited their use in conjunction with such base stocks.
  • PAG fluids are also polar and highly soluble in water, which can result in severe corrosion problems. Moreover, the formulation or additive response of PAG fluids can be unpredictable, rendering them difficult to formulate with.,
  • Polyethylene glycol, polypropylene glycol and polybutylene glycol are PAG fluids that are soluble in water, but very slightly soluble (e.g., Jess than about 0, 1 wt% at 23°C) in mineral and synthetic hydrocarbon-based base stocks.
  • PAG fluids contains two OH groups which may contribute to their reduced solubility in non-polar solvents such as hydrocarbon-based base stocks.
  • Rudnick in Synthetic Lubricants and High-Perfonnance Functional Fluids (2d Ed. 1999), Chapter 6, Polyalkylene Glycols, pp. 159- 193
  • Rudnick describes types of polyalkylene glycols used commercially as lubricants including, among others, "[hjomopolymers of propylene oxide (polypropylene glycols), which are the water-insoluble type” and “show limited solubility in oil", such as “monobutyl ethers” (p. 163).
  • Rudnick also describes "[copolymers of ethylene oxide and propylene oxide, which are the water-soluble type” and “are typically diols or monobutyl ethers” (p. 163). Rudnick also describes “[pjoiymers of butyiene oxide [which] show greater oil solubility than the homopolvmers of propylene oxide,” “[pjoiymers of propylene oxide and higher epoxides designed to give greater oil solubility” and “[pjoiymers of propylene oxide that are dimethyl ethers” (p. 164).
  • Other references which discuss polyalkylene glycols and related compounds are: U.S. 4,973,414, U.S. 5,024,678, U.S. 5,599,100,
  • One aspect of this invention relates to a lubricating composition, comprising in admixture at least 40 wt.% of a base stock selected from the group consisting of Group
  • Another aspect of this invention relates to a method of improving the triction and wear properties of a base s tock selected from the group consisting of Group I, Group II
  • the polyalkylene glycol mono ethers each have a molecular weight of from about 300 up to about 1200.
  • the polyalkylene glycol mono ethers are present in an amoun t of from about 1 wt% up to about 20 wt% of the composition.
  • the base stock of the lubricating composition is a Group IV base stock, or a blend of Group IV base stocks.
  • the kinematic viscosity at 100°C of the lubricating composition is from about 4 cSt up to about 20 cSt.
  • the additive in the lubricating composition is one or more chosen from the group consisting of friction modifiers, antiwear additives, viscosity improvers, detergents, dispersants, antioxidants, pour point depressants, anti-foam agents, demulsifiers, corrosion inhibitors, seal compatibility additives, antirust additives, and co-base stocks.
  • the additive or additives are present in an amount of up to about 20 wi% of the composition.
  • the additive is a friction modifier.
  • the lubricating composition further comprises a co-base stock.
  • the co-base stock is one or more chosen from the group consisting of esters and alkylated naphthalenes.
  • the polyalkylene glycol ether in the lubricating composition is polyethylene glycol monomethyl ether or polypropylene glycol monobutyl ether, or a combination thereof.
  • polyethylene glycol monomethyl ether represented by the formula:
  • the molecular weight can be up to about 5000.
  • polypropylene glycol monobutyl ether represented by the formula:
  • the molecular weight can be up to about 5000.
  • the single-capped polyalkylene glycols i.e., polyalkylene glycol mono ethers
  • polyalkylene glycol mono ethers i.e., polyalkylene glycol mono ethers
  • R] and R 2 optionally include -OH, -NH 2 , and/or -CHO functional groups. Exemplary embodiments can include those in which, R.
  • the molecular weights of the polyalkylene glycol mono ethers can be up to about 5000, for example up to about 4000, up to about 3000, up to about 2000, up to about 1200, up to about 900, up to about 600, or up to about 400. Additionally or alternately, the molecular weight can be from at least about 40, at least about 100, at least about 200, or at least about 300.
  • lubricating compositions comprising mineral and/or synthetic hydrocarbon-based base stocks and polyalkylene glycol mono ethers provide solvency for additive packages, and unexpected improvements in average coefficient of friction, average wear scar, average film thickness, cam and lifter wear, and phosphorus retention,
  • a lubricating composition made comprising polyaikylene glycol mono ethers is prepared by blending or admixing with a base stock, one or more polyaikylene glycol mono ethers and an additive package comprising an effective amount of at least one additional performance enhancing additive, such as for example but not limited to at least one of a friction modifier, and/or a lubricity agent, and/or an antiwear agent, and/or extreme pressure additives, and/or a viscosity index (VI) improver, and/or a detergent, and/or a dispersani, and/or an antioxidant, and/or a pour point depressant, and/or an antifoamant, and/or a demulsifier, and/or a corrosion inhibitor, and/or a seal swell control additive, and/or antiseizure agent, and/or dye, and/or metal deactivators, and/or antistaining agent, and/or a co-basestock.
  • additional performance enhancing additive such as
  • those additives common to most formulated lubricating oils include one or more friction modifiers, antiwear additives, detergents, dispersants, and antioxidants, with other additives being optional depending on the intended use of the oil.
  • An effective amount of one or more additives, or an additive package containing one or more such additives is added to, blended into or admixed with the base stock to meet one or more formulated product specifications, such as those relating to a lube oil for diesel engines, internal combustion engines, automatic transmissions, turbine or jet engines, as is known.
  • the polyaikylene glycol mono ether can be premixed with a pour point depressant. Applicants have discovered that this premixing results in improved pour point for the formulated lubricating composition.
  • the polyalkylene glycol mono ether may not be premixed with any of the additives,
  • the lubricating compositions of the present disclosure may use Group I, Group II or Group 111 base oil stocks, Group IV polyalphaolefin (PAO) base oil stocks, Group V base oil stocks, or any combination thereof.
  • Useful Group I-III, Group IV PAO and Group V base stocks have a Kvioo (kinetic viscosity at 100°C) of greater than about 2 cSt to about 25 cSt.
  • Groups I, II, III, IV and ⁇ ? are broad categories of base stocks developed and defined by the American Petroleum Institute (API Publication 1509; www iPI.org) to create guidelines for lubricant base oils.
  • Group I base stocks generally have a viscosity index of between about 80 to 120 and contain greater than about 0,03% sulfur and less than about 90% saturates.
  • Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
  • Group III stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03% sulfur and greater than about 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stocks are base stocks not included in Groups I-IV. Table 1 summarizes properties of each of these five groups.
  • Manufacturing plants that make Group I base stocks typically use solvents to extract the lower viscosity index (VI) components and increase the VI of the crude to the desired specifications. These solvents are typically phenol or furfural. Solvent extraction gives a product with less than 90% saturates and more than 300 ppm sulfur. The majority of lube production in the world is in the Group I category.
  • Manufacturing plants that make Group II base stocks typically employ hydroprocessing such as hydrocracking or severe hydrotreating to increase the VI of the crude oil to the specifications value. The use of hydroprocessing typically increases the saturate content above 90% and reduces the sulfur below 300 ppm. Approximately 10% of the lube base oil production in the world is in the Group ⁇ category, and about 30% of U.S. production is Group II.
  • Group III base stocks are usually produced using a three-stage process involving hydrocracking an oil feed stock, such as vacuum gas oil, to remove impurities and to saturate all aromatics which might be present to produce highly paraffinic lube oil stock of very high viscosity index, subjecting the hydrocracked stock to selective catalytic hydrodewaxing which converts normal paraffins into branched paraffins by isomerization followed by hydrofinishing to remove any residual aromatics, sulfur, nitrogen or oxygenates.
  • an oil feed stock such as vacuum gas oil
  • Group III stocks as used in the present specification and appended claims also embrace non-conventional or unconventional base stocks and/or base oils which include one or a mixture of base stoek(s) and/or base oil(s) derived from: (!
  • GTL Gas-to-Liquids
  • base stock(s) and/or base oil(s) derived from synthetic wax, natural wax or waxy feeds, waxy feeds including feeds such as mineral and/or non-mineral oil waxy feed stocks, for example gas oils, slack waxes (derived from the solvent de-waxing of natural oils, mineral oils or synthetic; e.g., Fischer-Tropsch feed stocks) and waxy stocks such as waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, foots oil or other natural, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials recovered from coal liquefaction or shale oil, linear or branched hydrocarbyl compounds with carbon number of about 20 or greater, preferably about 30 or greater, and mixtures of such base stocks and/or
  • GTL materials are materials thai are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconsiruetive processes from gaseous carbon-containing compounds, hydrogen-containing compounds, and/or elements as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks 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 feedstocks.
  • GTL base stoek(s) include oils boiling in the lube oil boiling range separated/fractionated from GTL materials such as by, for example, distillation or thermal diffusion, and subsequently subjected to well-known catalytic or solvent dewaxing processes to produce lube oils of reduced/low pour point; wax isomerates, comprising, for example, hydroisomerized or isodewaxed synthesized hydrocarbons; hydroisomerized or isodewaxed Fischer-Tropsch ("F-T") material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydroisomerized or isodewaxed F-T hydrocarbons or hydroisomerized or isodewaxed F-T waxes, hydroisomerized or isodewaxed synthesized waxes, or mixtures thereof.
  • F-T Fischer-Tropsch
  • GTL base stock(s) derived from GTL materials especially, hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax derived base stock(s) are characterized typically as having kinematic viscosities at 100°C of from about 2 mm 2 /s to about 50 mm 2 /s, preferably from about 3 rnnr/s to about 50 mm7s, more preferably from about 3.5 rnnr/s to about 30 mrrrVs, as exemplified by a GTL base stock derived by the isodewaxing of F-T wax, which has a kinematic viscosity of about 4 mm 2 /s at 100°C and a viscosity- index of about 130 or greater.
  • GTL base oil/base stock and/or wax isomerate base oil/base stock as used herein and in the claims is to be understood as embracing individual fractions of GTL base stock/base oil or wax isomerate base stock/base oil as recovered in the production process, mixtures of two or more GTL base stocks/base oil fractions and/or wax isomerate base stocks/base oil fractions, as well as mixtures of one or two or more low viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fractions) with one, two or more high viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) to - i l - produce a bi-modal blend wherein the blend exhibits a viscosity within the aforesaid recited range.
  • Reference herein to Kinematic Viscosity refers to a measurement made by A STM method D445.
  • GTL base stocks derived from GTL materials especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s), such as wax hydroisomerat.es/isodewaxates, which can be used as base stock components of this invention are further characterized typically as having pour points of about -5°C or lower, preferably about -10°C or lower, more preferably about -15°C or lower, still more preferably about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower. If necessary, a separate dewaxing step may be practiced to achieve the desired pour point.
  • References herein to pour point refer to measurement made by ASTM D97 and similar automated versions.
  • the GTL base stock(s) derived from GTL materials, especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s) which are base stock components which can be used in this invention are also characterized typically as having viscosity indices of 80 or greater, preferably 100 or greater, and more preferably 120 or greater. Additionally, in certain particular instances, viscosity index of these base stocks may be preferably 130 or greater, more preferably 135 or greater, and even more preferably 140 or greater.
  • GTL base stock(s) that derive from GTL materials preferably F-T materials especially F-T wax generally have a viscosity index of 130 or greater. References herein to viscosity index refer to ASTM method D2270.
  • the GTL base stock(s) are typically highly paraffinic of greater than 90 percent saturates) and may contain mixtures of monoeycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
  • the ratio of the naphfhenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stocks typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock and base oil obtained by the hydroisomerization/isodewaxing of F-T material, especially F-T wax is essentially nil.
  • the GTL base stock(s) comprises paraffinic materials thai consist predominantly of non-cyclic isoparaffins and only minor amounts of cycloparaffins.
  • These GTL base stock(s) typically comprise paraffinic materials that consist of greater than 60 wt.% non-cyclic isoparaffins, preferably greater than 80 wt% non-cyclic isoparaffins, more preferably greater than 85 wt% non-cyclic isoparaffins, and most preferably greater than 90 wt% non-cyclic isoparaffins.
  • compositions of GTL base stock(s), hydroisomerized or isodewaxed F-T material derived base stock(s), and wax-derived hydroisomerized/isodewaxed base stock(s), such as wax isomerates/isodewaxates are recited in U.S. 6,080,301: U.S. 6,090,989, and U.S. 6,165,949, for example.
  • Base stock(s) derived from waxy feeds which are also suitable for use as the Group III stocks in this invention, are paraffinic fluids of lubricating viscosity derived from hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed waxy feed stocks of mineral oil, non-mineral oil, non-petroleum, or natural source origin, e.g.
  • feed stocks such as one or more of gas oils, slack wax, waxy fuels hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocrackat.es, thermal crackates, foots oil, wax from coal liquefaction or from shale oil, or other suitable mineral oil, non-mineral oil, non-petroleum, or natural source derived waxy materials, linear or branched hydrocarbyl compounds with carbon number of about 20 or greater, preferably about 30 or greater, and mixtures of such isomerate/isodewaxate base stock(s).
  • gas oils such as one or more of gas oils, slack wax, waxy fuels hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocrackat.es, thermal crackates, foots oil, wax from coal liquefaction or from shale oil, or other suitable mineral oil, non-mineral oil, non-petroleum, or natural source derived waxy materials, linear or branched hydrocarbyl
  • Slack wax is the wax recovered from any waxy hydrocarbon oil including synthetic oil such as F-T waxy oil or petroleum oils by solvent or auto-refrigerative dewaxing.
  • Solvent dewaxing employs chilled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, mixtures of MEK and toluene, while auto-refiigerative dewaxing employs pressurized, liquefied low boiling hydrocarbons such as propane or butane.
  • Slack waxes secured from synthetic waxy oils such as F-T waxy oil will usually have zero or nil sulfur and/or nitrogen containing compound content.
  • Slack wax(es) secured from petroleum oils may contain sulfur and nitrogen-containing compounds.
  • Such heteroatom compounds must be removed by hydrotreating (and not hydrocracking), as for example by hydrodesulfurization (HDS) and hydrodenitrogenation (HD ) so as to avoid subsequent poisoning, 7 deactivation of the bydroisomerization catalyst.
  • the process of making the lubricant oil base stocks from wax or waxy stocks may be characterized as an isomerization process.
  • slack waxes may need to be subjected to a preliminary hydrotreating step under conditions already well known to those skilled in the art to reduce (to levels that would effectively avoid poisoning or deactivating the isomerization catalyst) or to remove sulfur- and nitrogen-containing compounds which would otherwise deactivate the hydroisomerization or hydrodewaxing catalyst used in subsequent steps.
  • F-T waxes are used, such preliminary treatment is not required because such waxes have only trace amounts (less than about 10 ppm, or more typically less than about 5 ppm to nil each) of sulfur and/or nitrogen compound content.
  • some hydrodewaxing catalyst feed F-T waxes may benefit from prehydrotreatment for the removal of oxygenates while others may benefit from oxygenates treatment.
  • the hydroisomerization or hydrodewaxing process may be conducted over a combination of catalysts, or over a single catalyst.
  • the hydroprocessing used for the production of base stocks from such waxy feeds may use an amorphous hydrocracking/liydfoisomerization catalyst, such as a lube hydrocracking (LHDC) catalysts, for example catalysts containing Co, Mo, i, W, Mo, etc., on oxide supports, e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeoiitic catalyst.
  • LHDC lube hydrocracking
  • Hydrocarbon conversion catalysts useful in the conversion of the n-paraffm waxy feedstocks disclosed herein to form the isoparaffmic hydrocarbon base oil are zeolite catalysts, such as ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, offretite, ferrierite, zeolite beta, zeolite t eta, and zeolite alpha, as disclosed in U.S. 4,906,350. These catalysis are used in combination with Group VIII metals, in particular palladium or platinum. The Group VIII metals may be incorporated into the zeolite catalysts by conventional techniques, such as ion exchange,
  • Conversion of the waxy feed stock may be conducted over a combination of Pt/zeolite beta and Pi/ZSM-23 catalysts or over such catalysts used in series in the presence of hydrogen.
  • the process of producing the lubricant oil base stocks comprises hydroisomerization and dewaxing over a single catalyst, such as Pt/ZSM-35.
  • the waxy feed can be fed over a catalyst comprising Group VIII metal loaded ZSM-48, preferably Group VIII noble metal loaded ZSM-48, more preferably Pi/ZSM-48 in either one stage or two stages.
  • useful hydrocarbon base oil products may be obtained.
  • Catalyst ZSM-48 is described in U.S. 5,075,269.
  • a dewaxing step when needed, may be accomplished using one or more of solvent dewaxing, catalytic dewaxing or hydrodewaxing processes or combinations of such processes in any sequence.
  • the hydroisomerate may be contacted with chilled solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of ME/MIBK, or mixtures of ME /toluene and the like, and further chilled to precipitate out the higher pour point material as a waxy solid which is then separated from the solvent-containing lube oil fraction which is the raffinate.
  • the raffinate is typically further chilled in scraped surface chillers to remove more wax solids.
  • Auio-refrigerative dewaxing using low molecular weight hydrocarbons, such as propane can also be used in which the hydroisomerate is mixed with, e.g., liquid propane, at least a portion of which is flashed off to chili down the hydroisomerate to precipitate out the wax.
  • the wax is separated from the raffinate by filtration, membrane separation or cen rifugation. Tlie solvent is then stripped out of the raffinate, which is then fractionated to produce the preferred base stocks useful in the present invention.
  • catalytic dewaxing In catalytic dewaxing the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate. Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling materials which are separated from the heavier base stock fraction. This base stock fraction can then be fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fractionation of the heavy base stock fraction material into the desired base stocks.
  • Any dewaxing catalyst which will reduce the pour point of the hydroisomerate and preferably those which provide a large yield of lube oil base stock from the hydroisomerate may be used.
  • These include shape selective molecular sieves which, when combined with at least one catalytic metal component, have been demonstrated as useful for dewaxing petroleum oil tractions and include, for example, ferrierite, mordenite, ZSM-5, ZSM-1 1 , ZSM-23, ZSM-35, ZSM-22 also known as theta one or TON, and the silicoaluminophosphates known as SAPOs.
  • a dewaxing catalyst which has been found to be unexpectedly particularly effective comprises a noble metal, preferably Pt, composited with H-mordenite.
  • the dewaxing may be accomplished with the catalyst in a fixed, fluid or slurry bed.
  • Typical dewaxing conditions include a temperature in the range of from about 400 to 600°F, a pressure of 500 to 900 psig, H 2 treat rate of 1500 to 3500 SCF/B for flow-through reactors and LHSV of 0.1 to 10, preferably 0.2 to 2.0.
  • the dewaxing is typically conducted to convert no more than 40 wt.% and preferably no more than 30 wt% of the hydroisomerate having an initial boiling point in the range of 650 to 750°F to material boiling below its initial boiling point.
  • PAO Polyalpha olefin
  • base stocks may also be used in the present invention.
  • PAOs in general are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of polyalphaolefins which include, but are not limited to, C? to about C ? alphaoiefms, with the Cg to about C j 6 alphaoiefms, such as 1-octene, 1 -decene, 1-dodecene and the like, being preferred.
  • the preferred polyaiphaoiefins are poly-l-octene, poly-l-decene and poly- 1 -dodecene and mixtures thereof and mixed olefm-derived polyolefins.
  • the PAO fluids may be conveniently made by the polymerization of one or a mixture of alphaolefins in the presence of a polymerization catalyst such as the Friedel-Crafts catalyst including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanoi, carboxylic acids or esters such as ethyl acetate or ethyl proprionate.
  • a polymerization catalyst such as the Friedel-Crafts catalyst including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanoi, carboxylic acids or esters such as ethyl acetate or ethyl proprionate.
  • a polymerization catalyst such as the Friedel-Crafts catalyst including, for example, aluminum trichloride,
  • Patents 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413, 156; 4,434,408; 4,910,355; 4,956, 122; and 5,068,487.
  • the dimers of the C i4 to C i8 olefins are described in U.S. 4,218,330.
  • PAOs useful in the present invention may have a kinematic viscosity at 100°C from about 1.5 to about 5,000 cSt (mm 2 /s).
  • the PAO preferably has a kinematic viscosity at 100°C from about 2 to about 25 cSt (mm7s), from about 2 to about 20 cSt, or from about 2 to about 15 cSt.
  • PAOs are often identified by reference to their approximate kinematic viscosity at 100°C.
  • PAO 6 refers to a PAO with a kinematic viscosity of approximately 6 cSt at 100°C
  • the PAOs useful in the present invention can also be made by metallocene catalysis.
  • the metallocene-catalyzed PAO can be a copolymer made from at least two or more different alphaolefins, or a homo-polymer made from a single alphaolefin feed employing a metallocene catalyst system.
  • the metallocene catalyst can be simple metallocenes, substituted metallocenes or bridged metallocene catalysts activated or promoted by, for instance, methylaluminoxane (MAO) or a non-coordinating anion, such as ⁇ , ⁇ -dimethyianiliniurn tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anion.
  • MAO methylaluminoxane
  • a non-coordinating anion such as ⁇ , ⁇ -dimethyianiliniurn tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anion.
  • the copolymer mPAO composition is made from at least two alphaolefins of C 3 to C 30 range and having monomers randomly distributed in the polymers. It is preferred that the average carbon number is at least 4.1.
  • ethylene and propylene, if present in the feed, are present in the amount of less than 50 wt% individually or preferably less than 50 wt% combined.
  • the copolymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate taciticity.
  • mPAO can also be made from mixed feed Linear Alpha Olefins (LAOs) comprising at least two and up to 26 different linear alphaolefins selected from C3 to C3 linear alphaolefins.
  • LAOs Linear Alpha Olefins
  • the mixed feed LAO can be obtained, for example, from an ethylene growth processing using an aluminum catalyst or a metailocene catalyst.
  • the growth olefins comprise mostly Ce to C i* LAO. LAOs from other processes can also be used.
  • the homo-polymer mPAO composition can be made from single alphaolefin chosen from alphaolefins in the C 3 to C 30 range, preferably C 3 to C-.e, most preferably € " 3 to C i4 or C 3 to Ci2.
  • the homo-polymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate taciticity. The taciticity can be carefully tailored by the polymerization catalyst and polymerization reaction condition chosen or by the hydrogenation condition chosen.
  • the alphaoiefin(s) can be chosen also from any component from a conventional LAO production facility or from a refinery. It can be used alone to make homo -polymer or together with another LAO available from a refinery or chemical plant, including propylene, 1 -butene, 1-pentene, and the like, or with 1-hexene or 1 -octene made from a dedicated production facility.
  • the alphaolefins also can be chosen from the alphaolefins produced from Fischer-Tropsch synthesis (as reported in U.S. 5,382,739).
  • C 3 to Cje alphaolefins are suitable to make homo-polymers.
  • Other combinations such as C 4 - and C 14 -LAO, Ce- and C16-LAO, C 8 -, Cio-, C 12-LAO, or Cs- and C i4 -LAO, C 6 -, C10-, C i4 -LAO, C 4 - and C i2 -LAO, etc., are suitable to make copolymers.
  • a feed comprising a mixture of LAOs selected from C 3 to C30 LAOs or a single LAO selected from C 3 to Cie LAO, is contacted with an activated metallocene catalyst under oligomerization conditions to provide a liquid product suitable for use in lubricant components or as functional fluids.
  • copolymer compositions made from at least two alphaolefins of C 3 to C 0 range and having monomers randomly distributed in the polymers.
  • the phrase "at least two alphaolefins” will be understood to mean “at least two different alphaolefins” (and similarly “at least three alphaolefins” means “at least three different alphaolefins", and so forth).
  • the product obtained is an essentially random liquid copolymer comprising the at least two alphaolefins.
  • essentially random is meant that one of ordinary skill in the art would consider the products to be random copolymer.
  • liquid will be understood by one of ordinary skill in the art as meaning liquid under ordinary conditions of temperature and pressure, such as ambient temperature and pressure.
  • the process for producing mPAO employs a catalyst system comprising a metallocene compound (Formula 1 , below) together with an activator such as a non- coordinating anion ( CA) (Formula 2, below) or mefhylaluminoxane (MAO) 1 11 1 (Formula 3, below):
  • a metallocene compound Formmula 1 , below
  • an activator such as a non- coordinating anion ( CA) (Formula 2, below) or mefhylaluminoxane (MAO) 1 11 1 (Formula 3, below):
  • catalyst system is defined herein to mean a catalyst precursor/activator pair, such as a metallocene/activator pair.
  • catalyst system When “catalyst system” is used to describe such a pair before activation, it means the un activated catalyst (precatalvst) together with an activator and, optionally, a co-activator (such as a trialkyl aluminum compound).
  • a co-activator such as a trialkyl aluminum compound
  • this activated "catalyst system” may optionally comprise the co-activator and/or other charge -balancing moiety.
  • the co-activator such as trialkyl aluminum compound, is also used as an impurity scavenger.
  • the metallocene is selected from one or more compounds according to Formula 1 above.
  • M is selected from Group 4 transition metals, preferably zirconium (Zr), hafnium (Hi) and titanium (Ti), LI and L2 are independently selected from cyciopentadienyl ("Cp"), indenyl, and fluorenyl, which may be substituted or unsubstituted, and which may be partially hydrogenated.
  • A is an optional bridging group which, if present, can he selected from diaikvlsilyl, dialk imeihyl, diphenyisilyi or diphenylm ethyl, ethyl enyl (— CH 2 -CH 2 ), alkylethylenyl (— CR 2 -CR 2 ), where alkyl can be independently C j to C ie alkyl radical or phenyl, tolyf, xylyl radical and the like, and wherein each of the two X groups, Xa and Xb, are independently selected from halides OR (R is an alkyl group, preferably selected from Q to C 5 straight or branched chain alkyl groups), hydrogen, Ci to Cie alkyl or aryl groups, haloalkyl, and the like. Usually relatively more highly substituted metallocenes give higher catalyst productivity and wider product viscosity ranges.
  • the polyalphaolefins preferably have a Bromine number of 1.8 or less as measured by ASTM D 1 159, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1 .4 or less, preferably 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less. If necessary the polyalphaolefins can be hydrogenated to achieve a low bromine number.
  • mpolyaiphaoiefins described herein may have monomer units represented by Formula 4 in addition to the all regular 1,2-connection:
  • n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton MR.
  • Any of the mpolyaiphaoiefins (mPAO) described herein may have an Mw (weight average molecular weight) of 100,000 or less, preferably between 100 and 80,000, preferably between 250 and 60,000, preferably between 280 and 50,000, preferably between 336 and 40,000 g mol.
  • any of the mpolyalphaolefins (mPAO) described herein may have a M (number average molecular weight) of 50,000 or less, preferably between 200 and 40,000, preferably between 250 and 30,000, preferably between 500 and 20,000 g/mol,
  • any of the mpolyalphaolefins (mPAO) described herein may have a molecular weight distribution (MWD-Mw/Mn) of greater than 1 and less than 5, preferably less than 4, preferably less than 3, preferably less than 2.5, The MWD of mPAO is always a function of fluid viscosity.
  • any of the polyalphaolefms described herein may have an Mw/Mn of between 1 and 2.5, alternately between 1 and 3.5, depending on fluid viscosity.
  • GPC solvent was HPLC Grade tetrahydrofuran, uninhibited, with a column temperature of 30°C, a flow rate of 1 mi/min, and a. sample concentration of 1 wt%, and the Column Set is a Phenogel 500 A, Linear, 10E6A.
  • any of the m-polyalphaolefins (mPAO) described herein may have a substantially minor portion of a high end tail of the molecular weight distribution.
  • the mPAO has not more than 5.0 wt% of polymer having a molecular weight of greater than 45,000 Daltons. Additionally or alternately, the amount of the mPAO that has a molecular weight greater than 45,000 Daltons is not more than 1.5 wt%, or not more than 0.10 wt.%.
  • the amount of the mPAO that has a molecular weight greater than 60,000 Daltons is not more than 0,5 wt%, or not more than 0.20 wt%, or not more than 0.1 wt%.
  • the mass fractions at molecular weights of 45,000 and 60,000 can be determined by GPC, as described above.
  • Any mPAO described herein may have a pour point of less than ()°C (as measured by ASTM D97), preferably less than ⁇ 10°C, preferably less than -20°C, preferably less than -25°C, preferably Jess than -30°C, preferably less than -35°C, preferably less than -50°C, preferably from -10°C to -80°C, preferably from ⁇ 15°C to -70°C.
  • mPolyalphaolefins (mPAO) made using metallocene catalysis may have a kinematic viscosity at 100°C from about 1.5 to about 5,000 cSt (mm 2 /s).
  • the mPAO preferably has a kinematic viscosity ax 100°C from about 2 to about 25 cSt (mm ? 7s), from about 2 to about 20 cSt, or from about 2 to about 15 cSt.
  • the lubricating compositions of the present disclosure also contain at least one additive, as described below.
  • the use of polyalkylene glycol mono ethers greatly improves the solubility of additives in lubricating compositions when compared to the solubility of additives when using polyalkylene glycols which are not single-capped.
  • the lubricant compositions are not limited by the examples shown herein as illustrations.
  • a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present invention if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this invention. Friction modifiers may include metal-containing compounds or materials as well as ashless compounds or materials, or mixtures thereof.
  • Metal-containing friction modifiers may include metal salts or metal-ligand complexes where the metals may include alkali, alkaline earth, or transition group metals. Such metal-containing friction modifiers may also have low-ash characteristics. Transition metals may include Mo, 8b, So, Fc, Cu, Zn, and others. Ligands may include hydrocarby!
  • Mo-containing compounds can be particularly effective such as for example Mo-dithiocarbamat.es, Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am), Mo-alcoholates, Mo-alcohol-amides, etc. See U.S. 5,824,627; U.S. 6,232,276: U.S. 6, 153,564; U.S. 6, 143,701 : U.S. 6, 110,878: U.S. 5,837,657: U.S. 6,010,987; U.S. 5,906,968; U.S. 6,734, 150; U.S. 6,730,638; U.S. 6,689,725; U.S. 6,569,820; WO 99/66013 ; WO 99/47629; WO 98/26030.
  • Ashless friction modifiers may include lubricant materials that contain effective amounts of polar groups, for example, hydroxyl-containing hydrocarby! base oils, glycerides, partial glycerides, glyceride derivatives, and the like.
  • Polar groups in friction modifiers may include hydrocarbyl groups containing effective amounts of O, N, S, or P, individually or in combination.
  • Other friction modifiers that may be particularly effective include, for example, salts (both ash- containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and comparable synthetic long-chain hydrocarby! acids, a!coho!s, amides, esters, hydroxy carboxylates, and the like.
  • fatty organic acids, fatty amines, and su!furized fatty acids may be used as suitable friction modifiers.
  • Useful concentrations of friction modifiers may range from about 0.01 wt% to 10-15 wt% or more, often with a preferred range of about 0.1 wt% to 5 wt%. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, and often with a preferred range of about 20-2000 ppm, and in some instances a more preferred range of about 30-1000 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this invention. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
  • ZDDP zinc dialkyldithiophosphate
  • ZDDP compounds generally are of the formula ZniSP(S)(OR ] )(OR z )] 2 where R 1 and R z are Ci-Cj8 alkyl groups, preferably C 2 -Ci 2 alkyl groups. These alkyl groups may be straight chain or branched.
  • the ZDDP is typically used in amounts of from about 0.4 to 1.4 wt% of the total lube oil composition, although more or less can often be used advantageously.
  • Another way to minimize this effect is to replace some or all of the ZDDP with phosphorus-free antiwear additives.
  • Sulfurized olefins are useful as antiwear and EP additives.
  • Sulfur-containing olefins can be prepared by sulfurization or various organic materials including aliphatic. arylaliphatic or alicyclic olefinic hydrocarbons containing from about 3 to 30 carbon atoms, preferably 3-20 carbon atoms.
  • the olefinic compounds contain at least one non-aromatic double bond. Such compounds are defined by the formula
  • R 3 R 4 C CR 5 R 6 where each of R 3 -R" are independently hydrogen or a hydrocarbon radical.
  • Preferred hydrocarbon radicals are aikyi or alkenyl radicals. Any two of R'-R° may be connected so as to form a cyclic ring. Additional information concerning siilfurized olefins and their preparation can be found in U.S. 4,941,984,
  • alkylthiocarbamoyl compounds bis(dibutyl)thiocarbamoyl, for example
  • a molybdenum compound oxymolybdenum diisopropylphosphorodithioate sulfide, for example
  • a phosphorous ester dibutyl hydrogen phosphite, for example
  • U.S. 4,758,362 discloses use of a carbamate additive to provide improved antiwear and extreme pressure properties.
  • the use of thiocarbamate as an antiwear additive is disclosed in U.S. 5,693,598.
  • Thiocarbamate/molybdenum complexes such as moly-sulfur alkyl dithiocarbamate trimer complex is alkyl are also useful antiwear agents.
  • the use or addition of such materials should be kept to a minimum if the object is to produce low SAP formulations.
  • Esters of glycerol may be used as antiwear agents.
  • mono-, dk and tri-oleates, mono-palmitates and mono-myristates may be used.
  • ZDDP is combined with other compositions that provide antiwear properties.
  • U.S. 5,034, 141 discloses that a combination of a thiodixanthogen compound (octyithiodixanfhogen, for example) and a metal thiophosphate (ZDDP, for example) can improve antiwear properties.
  • U.S. 5,034,142 discloses that use of a metal alkyoxyalkylxanthate (nickel ethoxyethylxant ate, for example) and a dixanthogen (diethoxyethyl dixanthogen, for example) in combination with ZDDP improves antiwear properties.
  • Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphates and/or sulfur, nitrogen, boron, molybdenum phosphorodithioat.es, molybdenum dithioearbamates and various organo-molybdenum derivatives including heterocyclics, for example dimereaptothiadiazoles, mercaptobenzothiadiazoles, triazines, and the like, alicyclics, amines, alcohols, esters, diols, triols, fatty amides and the like can also be used.
  • Such additives may be used in an amount of about 0.01 to 6 wt%, preferably about 0.01 to 4 wt%.
  • ZDDP-Iike compounds provide limited hydroperoxide decomposition capability, significantly below that exhibited by compounds disclosed and claimed in this patent and can therefore be eliminated from the formulation or, if retained, kept at a minimal concentration to facilitate production of low SAP formulations.
  • Viscosity improvers also known as Viscosity Index modifiers, and VI improvers
  • Viscosity Index modifiers also known as Viscosity Index modifiers, and VI improvers
  • These additives increase the viscosity of the oil composition at elevated temperatures which increases film thickness, while having limited effect on viscosity at low temperatures.
  • Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are between about 1,000 to 1 ,000,000, more typically about 2,000 to 500,000, and even more typically between about 25,000 and 100,000.
  • suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutyiene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polvmethacrylate (copolymers of various chain length alkyl inethacryiates, for example), some formulations of which also serve as pour point depressants.
  • suitable viscosity index improvers include copolymers of ethylene and propylene, liydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chairs length acrylates, for example). Specific examples include styrene-isoprene or styrene- butadiene based polymers of 50,000 to 200,000 molecular weight.
  • the amount of viscosity modifier may range from 0.01 to 8 wt%, preferably 0.01 to 4 wt%, more preferably 0.01 to 2 wt% based on active ingredient and depending on the specific viscosity modifier used.
  • Detergents are commonly used in lubricating compositions.
  • a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • Salts that, contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TB , as measured by ASTM D2896) of from 0 to 80.
  • TB total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • a metal compound a metal hydroxide or oxide, for example
  • an acidic gas such as carbon dioxide
  • Useful detergents can be neutral, mildly overbased, or highly overbased.
  • the overbased material has a ratio of metallic ion to anionic portion of the detergent of about 1.05: 1 to 50: 1 on an equivalent basis. More preferably, the ratio is from about 4: 1 to about 25: 1.
  • Tlie resulting detergent is an overbased detergent that will tvpicallv have a TBN of about 150 or higher, often about 250 to 450 or more.
  • the overbasing cation is sodium, calcium, or magnesium.
  • a mixture of detergents of differing TBN can be used in the present invention.
  • Preferred detergents include the alkali or alkaline earth metal salts of sulfonates, phenates, carboxylates, phosphates, and salicylates.
  • Sulfonates may be prepared from sulfonic acids that are typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons.
  • Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (chlorobenzene, chlorotoluene, and cbloronapbthalene, for example).
  • the alkylating agents typically have about 3 to 70 carbon atoms.
  • the alkaryl sulfonates typically contain about 9 to about 80 carbon or more carbon atoms, more typically from about 16 to 60 carbon atoms.
  • Klamann in Lubricants and Related Products, op cit discloses a number of overbased metal salts of various sulfonic acids which are useful as detergents and dispersants in lubricants.
  • Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkyl phenol or sulfurized alkylphenol include straight chain or branched ( ' ⁇ ⁇ ( ' . ⁇ ,, alkyl groups, preferably, C4 -C20. Examples of suitable phenols include isobutyiphenoi, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the su!furizcd phenol with an alkaline earth metal base.
  • Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least Cn, preferably Co or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function.
  • M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction. See U.S. 3,595,79! for additional information on synthesis of these compounds.
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as detergents.
  • Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. 6,034,039, for example.
  • Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents).
  • the total detergent concentration is about 0.01 to about 8.0 wt%, preferably, about 0.1 to 4.0 wt%.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants may be ashless or ash-forming in nature.
  • the dispersani 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 chains contain 50 to 400 carbon atoms.
  • dispersants may be characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives
  • a particularly useful class of dispersants are the alkenylsuecinic 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 normally a polyisobutylene group.
  • Exemplary U.S. patents describing such dispersants are 3, 172,892; 3,215,707; 3,219,666; 3,316,177; 3,341 ,542; 3,444, 170; 3,454,607; 3,541,012; 3,630,904; 3,632,51 1 ; 3,787,374 and 4,234,435.
  • Other types of dispersant are described in U.S.
  • a further description of dispersants may be found, for example, in European Patent Application No, 471 071, to which reference is made for this purpose.
  • Hydrocarbyl-substituted succinic acid compounds are popular dispersants.
  • suecinimide, 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 alkenyl succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1 : 1 to about 5: 1. Representative examples are shown in U.S. Patents 3,087,936; 3, 172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1 ,094,044,
  • Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyois. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of an alkenyl succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U.S. 4,426,305.
  • the molecular weight of the alkenyl succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants.
  • the dispersants can be boraied with from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. 4,767,551. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be pari of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500, Representative examples are shown in U.S. Patents 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953 ; 3,798,165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products usefui in this invention can be prepared from high molecular weight alkyl- substituted hydroxyaromatics or HN(R) 2 group-containing reactants.
  • Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols. 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, polybutylene, and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600- 100,000 molecular weight.
  • an alkylating catalyst such as BF 3
  • HN(R) 2 group-containing reactants are alkylene pofyamines, principally polyethylene polyamines.
  • Other representative organic compounds containing at least one HN(R) 2 group suitable for use in the preparation of Mannich condensation products are well known and include the mono- and di-amino alkanes and their substituted analogs, e.g., efhyiamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholme, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.
  • alkylene polyamide reactants include ethylenediamine, (Methylene tri amine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene decamine, and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula H 2 N-Z-NH-) n H, mentioned before, Z. is a divalent ethylene and n is 1 to 10 of the foregoing formula.
  • propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as diehloro alkanes.
  • the alkylene polyamines 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 polyamine reactants,
  • Aldehyde reactants useful in the preparation of the high molecular products useful in this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol ( ⁇ -hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. 3,275,554; 3,438,757; 3,565,804; 3,755,433; 3,822,209 and 5,084, 197.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polvisobutylene having a Mn of from about 500 to about 5000 or a mixture of such hydrocarbylene groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkyiphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in an amount of about 0.1 to 20 wt%, preferably about 0.1 to 8 wt%.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cit, and U.S. Patents 4,798,684 and 5,084,197, for example.
  • Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxy! group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxy! groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C '- alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyi phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodeeyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-meihyl-6-t-butyl- 4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono- phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant invention.
  • ortho-coupled phenols include: 2,2 '-bis(4-heptyl-6-t-butyl-phenol); 2,2 '-bis(4-octyl-6-t-butyl-phenol); and
  • Para-coupled bisphenols include for example 4,4 ' -bis(2,6-di-t-butyl phenol) and 4,4 ' -methylene-bis(2,6-di-t-butyl phenol).
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R 8 R 9 R 10 N where R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R i is H, alkyi, aryl or R i i S(0)xR 5 z where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyi 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 about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R y are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyf.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyi substiruent groups of at least about 6 carbon atoms.
  • Examples of aliphatic groups include hexyi, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyis and diphenyl phenyiene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present invention include: p,p ' -dioetyldiphenyiamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octyiphenyi- alpha-naphthyf amine.
  • Sulfurized alkyi phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • Another class of antioxidant used in lubricating oil compositions is oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil Examples of suitable copper antioxidants include copper dihydrocarbyl tl io- or dithio-pbospbates and copper salts of carboxylic acid (naturally occurring or synthetic). Other suitable copper salts include copper dithiacarbamates, sulphonates, phenates, and aceiyiacetonates. Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are know to be particularly useful.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%, more preferably zero to less than 1.5 wt%, most preferably zero.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricating compositions of the present invention to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamid.es, condensation products of haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarat.es, vinyl esters of fatty acids and ally! vinyl ethers.
  • Patents 1 ,815,022; 2,015,748; 2, 191 ,498; 2,387,501 ; 2,655,479; 2,666,746; 2,721 ,877; 2,721 ,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof.
  • Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • 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, po!ysiloxanes, 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 demuisifiers; usually the amount of these additives combined is less than 1 percent and often less than 0.1 percent. Corrosion Inhibitors
  • Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition.
  • Suitable corrosion inhibitors include thiadiazoles. See, for example, U.S. Patents 2,719, 125; 2,719, 126; and 3,087,932.
  • Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • 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 phthaiate, for example), and poiybutenyl succinic anhydride.
  • Such additives may be used in an amount of about 0.01 to 3 wt%, preferably about 0.01 to 2 wt%.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available; they are referred to in Klamann in Lubricants and Related Products, op cit.
  • antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphat.es, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0,01 to 1.5 wt%.
  • the lubricating oil compositions may also include one or more co-base stocks which provide further increased solubility of the polyalkylene glycol mono ethers and additives in the Group I, Group II, Group III and/or Group IV base stock.
  • Esters comprise a useful co-basestock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, aikenyi succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, aikenyi malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, aikenyi succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, ai
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyf sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyi phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those full or partial esters which are obtained by reacting one or more polyhydric alcohols (preferably the hindered polyols such as the neopentyl polyols e.g. neopentyl glycol, trimethylol ethane, 2-methyl- 2 -propyl- 1,3 -propanediol, trimethylol propane, pentaerythntol and dipentaeryt ' hritol) with alkanoic acids containing at least about 4 carbon atoms (preferably to C ?
  • polyhydric alcohols preferably the hindered polyols such as the neopentyl polyols such as the neopentyl polyols such as the neopentyl polyols e.g. neopentyl glycol, trimethylol ethane, 2-methyl- 2 -propyl- 1,3 -propanediol, tri
  • o acids such as saturated straight chain fatty acids including caprylic acid, capric acid, 1 auric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid).
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms.
  • Alkylated naphthalenes are also a useful co-basestock. The alkyl groups on the alkylated naphthalene preferably have from about 6 to 30 carbon atoms, with particular preference to about 12 to 18 carbon atoms.
  • a preferred class of alkylating agents are the olefins with the requisite number of carbon atoms, for example, the hexenes, heptenes, ocienes, nonenes, decenes, uiidecenes, dodecenes. Mixtures of the olefins, e.g. mixtures of C12-C20 or Cu-Cis olefins, are useful. Branched alkylating agents, especially oligomerized olefins such as the trimers, tetramers, pentamers, etc., of light olefins such as ethylene, propylene, the butyl enes, etc., are also useful.
  • Typical amounts of such additives useful in the present invention are shown in Table 1 below.
  • Anti-foam Agents 0.001-1 0.001 -0.1
  • Lubricating compositions are prepared by blending together or admixing one or more base stocks from the group consisting of Group I, Group ⁇ , Group III, Group IV, and Group V base stocks, one or more polyaikylene glycol mono ethers, and one or more additives.
  • the lubricating compositions can be used as automotive engine lubricants and commercial vehicle engine lubricants.
  • the lubricating compositions demonstrate superior performance with regard to average friction coefficient, average wear scar, average film thickness, cam and lifter wear, and phosphorus retention when compared to similar compositions thai do not contain polyaikylene glycol mono ethers.
  • the lubricating compositions can also be used as industrial lubricants.
  • the base stock can be Group I, Group II, Group III, Group IV, or Group V, or any combination of these base stocks. These base stocks, or combinations of these base stocks can be used in the lubricating compositions in amounts of up to about 99 wt% of the composition, up to about 95 wt% of the composition, up to about 90 wt.% of the composition, up to about 80 wt% of the composition, up to about 70 wt% of the composition, up to about 60 wt% of the composition, up to about 50 wt% of the composition, or up to about 40 wt% of the composition.
  • the base stocks can be used in the lubricating compositions in amounts of at least about 40 wt% of the composition, at least about 50 wt% of the composition, at least about 60 wt% of the composition, at least about 70 wt% of the composition, at least about 80 wt% of the composition, at least about 90 wt% of the composition, or at least about 95 wt% of the composition.
  • the base stocks can be used in the lubricating compositions in amounts of from about 40 wt% of the composition to about 99 wt% of the composition, from about 50 wt% of the composition to about 99 wt% of the composition, from about 60 wt% of the composition to about 99 wt% of the composition, from about 70 wt% of the composition to about 99 wt% of the composition, from about 75 wt% of the composition to about 99 wt% of the composition, from about 75 wt% of the composition to about 95 wt% of the composition, or from about 75 wt% of the composition to about 85 wt% of the composition.
  • the Group I, Group ⁇ , Group III, Group IV and Group V base stocks, or combinations of these base stocks can have a kinematic viscosity at 100°C of up to about 25 cSt, up to about 20 cSt, up to about 15 cSt, up to about 12 cSt, up to about 10 cSt, up to about 8 cSt, or up to about 6 cSt.
  • the Group I, Group ⁇ , Group III, Group IV and Group V base stocks, or combinations of these base stocks can have a kinematic viscosity at 100°C of at least about 2 cSt, at least about 4 cSt, or at least about 6 cSt.
  • the Group I, Group ⁇ , Group III, Group IV and Group V base stocks, or combinations of these base stocks can have a kinematic viscosity at 100°C of from about 2 cSt to about 25 cSt, from about 2. cSt to about 15 cSt, from about 2. cSt to about 12 cSt, from about 4 cSt to about 10 cSt, or from about 4 cSt to about 8 cSt.
  • the polyalkylene glycol mono ethers can be used in an amount of up to about 60 wt%, up to about 50 wt% of the composition, up to about 40 wt% of the composition, up to about 30 wt% of the composition, up to about 20 wt% of the composition, up to about 15 wt% of the composition, up to about 10 wt% of the composition, up to about 5 wt% of the composition, or up to about 3 wt% of the composition.
  • the polyalkylene glycol mono ethers can be used in an amount of from about 0,5 wt%, from about 1 wt% of the composition, from about 2 wt% of the composition, from about 5 wt% of the composition, or from about 10 wt% of the composition. Further additionally or alternately, the polyalkylene glycol mono ethers can be used in an amount of from about i to about 25 wt% of the composition, or from about 1 to about 15 wt% of the composition, or from about 1 to about 5 wt% of the composition, from about 5 to about 25 wt% of the composition, or from about 10 to about 20 wt% of the composition.
  • At least one of the performance additives of the lubricating compositions is a friction modifier. Additionally or alternately, at least one of the additives is an antiwear and/or extreme pressure (EP) additive.
  • the additive package is present in an amount of up to about 30 wt% of the composition, up to about 25 wt% of the composition, up to about 20 wt% of the composition, up to about 15 wt% of the composition, up to about 10 wt% of the composition, or up to about 5 wt% of the composition.
  • the lubricating compositions have improved frictionai properties, and, thus, improved efficiency.
  • the average friction coefficient of the lubricating compositions is less than about 0.15, less than about 0.14, less than about 0.13, less than about 0.12, less than about 0.11, or less than about 0.10.
  • the lubricating compositions have improved wear properties, as indicated by average wear scar.
  • the average wear scar of the lubricating compositions is less than about 150 microns, less than about 140 microns, or less than about 130 microns,
  • the lubricating compositions have improved average film thickness.
  • the average film thiclaiess of the lubricating compositions is greater than about 50%, greater than about 60%, greater than about 70%, or greater than about 80%.
  • Average friction coefficients, average wear scar and average film thicknesses can be measured by a High Frequency Reciprocating Rig (HFR ) test.
  • the FTFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR). The test equipment and procedure are similar to the ASTM D6079 method except the test oil temperature is raised from 32°C to 195°C at 2°C/minute, 400 g load, 60 Hz frequency, and 0,5 mm stroke length,
  • the lubricating compositions have improved cam and lifter wear, as measured in accordance with the Sequence IIIG engine test, ASTM D7320.
  • the cam and lifter wear is less than about 25 microns, or less than about 20 microns, or less than about 16 microns.
  • the lubricating compositions have improved phosphorus retention as measured in accordance with the Sequence IIIG engine test, ASTM D7320.
  • the phosphorus retention is greater than about 80%, or greater than about 85%, or greater than about 90%>.
  • the pour points of the lubricating compositions were measured according to the ASTM D97 standard.
  • the pour point of the lubricating compositions is less than about -30°C, or less than about -40°C.
  • the kinematic viscosities at 40°C of the lubricating compositions were measured according to the ASTM D445 standard.
  • the lubricating compositions have a kinematic viscosity at 40°C of from about 30 cSt to about 50 cSt, or from about 35 cSt to about 45 cSt.
  • the kinematic viscosities at 100°C of the lubricating compositions were measured according to the ASTM T3445 standard.
  • the lubricating compositions have a kinematic viscosity at I00 c C of up to about 25 cSt, up to about 20 cSt, up to about 15 cSt, up to about 12 cSt, up to about 10 cSt, up to about 8 cSt, or up to about 6 cSt.
  • the lubricating compositions have a kinematic viscosity at 1G0°C of at least about 2 cSt, at least about 4 cSt, or at least about 6 cSt.
  • the lubricating compositions have a kinematic viscosity at 100°C of from about 2 cSt to about 25 cSt, from about 2 cSt to about 15 cSt, from about 2 cSt to about 12 cSt, from about 4 cSt to about 10 cSt, or from about 4 cSt to about 8 cSt,
  • Table 3 shows that polyethylene glycol monomethyl ether (550 molecular weight (MW)) was soluble in Group I, Group II, Group III and PAO base stocks, and that polypropylene glycol monobutyl ether (340 molecular weight (MW)) was soluble in Group I, Group III and PAO base stocks. Table 3 also shows that polyethylene glycol was insoluble in Group I and PAO base stocks, that polypropylene glycol was insoluble in Group I, Group II and PAO base stocks, and that polybutylene glycol was insoluble in Group I and PAO base stocks. Each of the above glycols are available from Sigma-Aldrich Corp. (St. Louis, Missouri).
  • SYNALOX EPB-165 and SYNALOX 50-15B were insoluble in Group III base stocks.
  • SYNALOX EPB-165 is a water-soluble fluid that consists of random copolymers of ethyle e oxide and propylene oxide with a terminal butoxy group.
  • SYNALOX 50-15B is an alcohol started material containing oxyethylene and oxypropylene groups with a single terminal hydroxy! group having the structure:
  • SYNALOX EPB-165 and SYNALOX 50-15B are available from The Dow Chemical Company (Midland, Michigan). Finally, Table 3 shows that SYNALOX, EPB-165 is soluble in alkylated naphthalene.
  • a fully formulated 5W30 engine oil composition (Inventive Oil 1) was prepared by blending PAO 6 with a single-capped polyalkyiene glycol (polypropylene glycol monobutyl ether (PPG-MBE) (molecular weight 1000), available from Sigma-Aldrich. Corp. (St. Louis, Missouri)) in the amount of 2 wt% of the composition and a commercial 5W30 additive package with a treat rate of 17 wt% of the composition.
  • Comparative Oils 1, 2 and 3 were prepared by blending the components shown in Table 4.
  • Comparative Oil 2 contained 98 wt% PAO 6 and 2 wt% PPG-MBE, and had a friction coefficient of 0.151, a wear scar of 202 microns, and a film thickness of 32%.
  • Comparative Oil 3 contained 83% PAO 6 and 17 wt.% of a commercial additive package, and had a friction coefficient of 0.152, a wear scar of 187 microns, and a film thickness of 49%.
  • Inventive Oil 1 was the same as Comparative Oil 3, except that 2 wt% of PPG-MBE was added and PAO 6 was decreased by 2 wt% to 81 wt%.
  • Inventive Oil 1 had a friction coefficient of 0.131, a wear scar of 145.5 microns, and a film thickness of 61%.
  • Comparative Oil 2 which contained 2 wt% PPG-MBE and no additive package
  • Comparative Oil 3 which contained 17 wt% additive package and no PPG-MBE.
  • Fully formulated 5VV30 engine oil compositions (Inventive Oils 2 and 3) were prepared by blending PAO 6 with, a single-capped polyaikylene glycol (polyethylene glycol monomethyl ether (PEG-MME) (molecular weight 550), available from Sigma-Aldrich Corp. (St, Louis, Missouri)) in the amount of 2 wt% and 4 wt% of the composition and a commercial 5W30 additive package with a treat rate of 17 wt% of the composition.
  • Comparative Oils 4, 5, 6 and 7 were prepared by blending the components shown in Table 5.
  • Comparative Oil 5 contained 98 wt.% PAO 6 and 2 wt% PEG-MME, and had a friction coefficient of 0.197, a wear scar of 308 microns, and a film thickness of 4%.
  • Comparative Oil 6 contained 96 wt% PAO 6 and 4 wt% PEG-MME, and had a friction coefficient of 0.179, a wear scar of 312.5 microns, and a film thickness of 4%.
  • Comparative Oil 7 contained 83% PAO 6 and 17 wt% of a commercial additive package, and had a friction coefficient of 0.152, a wear scar of 187 microns, and a film thickness of 49%.
  • Inventive Oil 2 was the same as Comparative Oil 7, except that 2 wt% of PEG-MME was added and PAO 6 was decreased by 2 wt% to 81 wt%.
  • Inventive Oil 3 was the same as Comparative Oil 7, except that 4 wt% of PEG-MME was added and PAO 6 was decreased by 4 wt% to 79 wt%.
  • Inventive Oils 2 and 3 had friction coefficients of 0.097 and 0.122, wear scars of 139 and 12.3 microns, and film thicknesses of 84% and 87%, respectively.
  • Each of these properties was significantly better than either Comparative Oils 5 and 6 (which contained 2 and 4 wt% PEG-MME and no additive package) or Comparative Oil 7 (which contained 17 wt% additive package and no PEG-MME).
  • a fully formulated 5W30 engine oil composition (Inventive Oil 4) was prepared by adding a single-capped polyalkyfene glycol (polypropylene glycol monobutyl ether (PPG-MBE) (molecular weight 340), available from Sigma- Aldrich ⁇ . (St. Louis, Missouri)) in the amount of 5 wt% to Comparative Oil 8, which was a fully formulated commercial 5W30 engine oil.
  • PPG-MBE polypropylene glycol monobutyl ether
  • Comparative Oil 8 had a cam and lifter wear of 27 microns and a phosphorus retention of 85,6%. Surprisingly, Inventive Oil 4 had a cam and lifter wear of 15 microns (44% better) and a phosphorus retention of 90.4% (5% better). Each of these properties was significantly better than Comparative Oil 8, and demonstrated an unexpected synergistic effect when PPG-MBE is included in the presence of the additive package. It was also observed that the additives in the additive package remained soluble in inventive Oil 4 in the presence of 5 wt.% of PPG-MBE.
  • Blends of single-capped polyalkylene glycol polypropylene glycol monobut l ether (PPG-MBE) (molecular weight 340), available from Sigma-Aldrich Cosp. (St. Louis, Missouri)) with zinc dialkyldithiophosphate (ZDDP) in a lubricating oil were prepared as shown in Table 7.
  • PPG-MBE polypropylene glycol monobut l ether
  • ZDDP zinc dialkyldithiophosphate
  • HFRR High Frequency Reciprocating Rig
  • the HFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR).
  • the test equipment and procedure are similar to the ASTM D6079 method except the test oil temperature is raised from 32°C to 195°C at 2 c' C/minute, 400 g load, 60 Hz frequency, and 0.5 mm stroke length or 400 g load, 60 Hz frequency at constant temperature, such as 100°C or 60°C.
  • Phosphorus retention was measured in accordance with the Sequence TTIG engine test, ASTM D7320.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP12731280.9A 2011-06-30 2012-06-27 Schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern Withdrawn EP2726582A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161503001P 2011-06-30 2011-06-30
PCT/US2012/044304 WO2013003405A1 (en) 2011-06-30 2012-06-27 Lubricating compositions containing polyalkylene glycol mono ethers

Publications (1)

Publication Number Publication Date
EP2726582A1 true EP2726582A1 (de) 2014-05-07

Family

ID=46420578

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12731280.9A Withdrawn EP2726582A1 (de) 2011-06-30 2012-06-27 Schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern

Country Status (3)

Country Link
EP (1) EP2726582A1 (de)
SG (2) SG10201604800QA (de)
WO (1) WO2013003405A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2013239811B2 (en) * 2012-03-29 2016-04-14 American Chemical Technologies, Inc. Hydrocarbon-based lubricants with polyether
US8685905B2 (en) 2012-03-29 2014-04-01 American Chemical Technologies, Inc. Hydrocarbon-based lubricants with polyether
US20140194333A1 (en) * 2013-01-04 2014-07-10 Exxonmobil Research And Engineering Company Method for improving engine fuel efficiency
US10000721B2 (en) 2014-12-30 2018-06-19 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
US10781397B2 (en) 2014-12-30 2020-09-22 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
SG11201704101UA (en) * 2014-12-30 2017-07-28 Exxonmobil Res & Eng Co Lubricating oil compositions with engine wear protection
WO2016137880A1 (en) * 2015-02-26 2016-09-01 Dow Global Technologies Llc Enhanced extreme pressure lubricant formulations
FR3048977B1 (fr) * 2016-03-15 2020-02-07 Total Marketing Services Composition lubrifiante a base de polyalkylene glycols

Family Cites Families (123)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1815022A (en) 1930-05-03 1931-07-14 Standard Oil Dev Co Hydrocarbon oil and process for manufacturing the same
US2015748A (en) 1933-06-30 1935-10-01 Standard Oil Dev Co Method for producing pour inhibitors
US2191498A (en) 1935-11-27 1940-02-27 Socony Vacuum Oil Co Inc Mineral oil composition and method of making
US2443264A (en) 1944-02-19 1948-06-15 Standard Oil Dev Co Compounded lubricating oil
US2387501A (en) 1944-04-04 1945-10-23 Du Pont Hydrocarbon oil
US2471115A (en) 1946-09-19 1949-05-24 Standard Oil Dev Co Lubricating oil
US2526497A (en) 1946-09-19 1950-10-17 Standard Oil Dev Co Mineral lubricating oil containing polysulfides of thiophosphorous and thiophosphoric acid esters
US2655479A (en) 1949-01-03 1953-10-13 Standard Oil Dev Co Polyester pour depressants
US2591577A (en) 1950-03-28 1952-04-01 Standard Oil Dev Co Lubricating oil containing disulfide derivatives of organo-substituted thiophosphoric acids
US2721878A (en) 1951-08-18 1955-10-25 Exxon Research Engineering Co Strong acid as a polymerization modifier in the production of liquid polymers
US2721877A (en) 1951-08-22 1955-10-25 Exxon Research Engineering Co Lubricating oil additives and a process for their preparation
US2666746A (en) 1952-08-11 1954-01-19 Standard Oil Dev Co Lubricating oil composition
US2719126A (en) 1952-12-30 1955-09-27 Standard Oil Co Corrosion inhibitors and compositions containing same
US2719125A (en) 1952-12-30 1955-09-27 Standard Oil Co Oleaginous compositions non-corrosive to silver
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
US3087932A (en) 1959-07-09 1963-04-30 Standard Oil Co Process for preparing 2, 5-bis(hydrocarbondithio)-1, 3, 4-thiadiazole
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
NL137371C (de) 1963-08-02
US3322670A (en) 1963-08-26 1967-05-30 Standard Oil Co Detergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3250715A (en) 1964-02-04 1966-05-10 Lubrizol Corp Terpolymer product and lubricating composition containing it
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
NL145565B (nl) 1965-01-28 1975-04-15 Shell Int Research Werkwijze ter bereiding van een smeermiddelcompositie.
US3382291A (en) 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3756953A (en) 1965-10-22 1973-09-04 Standard Oil Co Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3751365A (en) 1965-10-22 1973-08-07 Standard Oil Co Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products
US3798165A (en) 1965-10-22 1974-03-19 Standard Oil Co Lubricating oils containing high molecular weight mannich condensation products
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
US3541012A (en) 1968-04-15 1970-11-17 Lubrizol Corp Lubricants and fuels containing improved acylated nitrogen additives
GB1244435A (en) 1968-06-18 1971-09-02 Lubrizol Corp Oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
GB1282887A (en) 1968-07-03 1972-07-26 Lubrizol Corp Acylation of nitrogen-containing products
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3454607A (en) 1969-02-10 1969-07-08 Lubrizol Corp High molecular weight carboxylic compositions
US3595791A (en) 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3652616A (en) 1969-08-14 1972-03-28 Standard Oil Co Additives for fuels and lubricants
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
GB1328636A (en) 1970-03-31 1973-08-30 Exxon Research Engineering Co Preparation of organic phosphoryl or phosphorothionyl disulphides
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
US3804763A (en) 1971-07-01 1974-04-16 Lubrizol Corp Dispersant compositions
US3787374A (en) 1971-09-07 1974-01-22 Lubrizol Corp Process for preparing high molecular weight carboxylic compositions
US3742082A (en) 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US3769363A (en) 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
US3876720A (en) 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4149178A (en) 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4454059A (en) 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
BR7800984A (pt) 1977-02-25 1979-01-02 Lubrizol Corp Composicao lubrificante;e concentrado para formulacao de composicoes lubrificantes
JPS54159411A (en) 1978-06-07 1979-12-17 Nippon Oil & Fats Co Ltd Engine oil composition
US4218330A (en) 1978-06-26 1980-08-19 Ethyl Corporation Lubricant
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4239930A (en) 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
JPS56126315A (en) 1980-03-11 1981-10-03 Sony Corp Oscillator
US4367352A (en) 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4426305A (en) 1981-03-23 1984-01-17 Edwin Cooper, Inc. Lubricating compositions containing boronated nitrogen-containing dispersants
US4956122A (en) 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
JPS5911397A (ja) 1982-06-09 1984-01-20 Idemitsu Kosan Co Ltd 疲労寿命改良潤滑剤
JPS61166892A (ja) 1984-12-14 1986-07-28 Nippon Oil Co Ltd 舶用デイ−ゼルエンジン用潤滑油組成物
US4767551A (en) 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US4758362A (en) 1986-03-18 1988-07-19 The Lubrizol Corporation Carbamate additives for low phosphorus or phosphorus free lubricating compositions
JPH06104640B2 (ja) 1986-05-20 1994-12-21 第一工業製薬株式会社 本質的に非芳香族系炭化水素化合物と相溶するポリオキシアルキレン化合物の製造方法
DE3711985A1 (de) 1987-04-09 1988-10-20 Union Rheinische Braunkohlen Verwendung von polyolethern zur verhinderung oder verminderung von ablagerungen in gemischaufbereitungssystemen
DE3718374A1 (de) 1987-06-02 1988-12-15 Bayer Ag Polyether, verfahren zu ihrer herstellung und schmiermittel, die diese polyether enthalten
US4798684A (en) 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
FR2626005A1 (fr) 1988-01-14 1989-07-21 Shell Int Research Procede de preparation d'une huile lubrifiante de base
DE68912454T2 (de) 1988-07-21 1994-05-11 Bp Chem Int Ltd Polyetherschmiermittel.
US4910355A (en) 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
US4941984A (en) 1989-07-31 1990-07-17 The Lubrizol Corporation Lubricating oil compositions and methods for lubricating gasoline-fueled and/or alcohol-fueled, spark-ignited engines
US5034141A (en) 1989-09-07 1991-07-23 Exxon Research And Engineering Company Lubricating oil containing a thiodixanthogen and zinc dialkyldithiophosphate
US5034142A (en) 1989-09-07 1991-07-23 Exxon Research And Engineering Company Lubricating oil containing a nickel alkoxyalkylxanthate, a dixanthogen, and zinc dialkyldithiophosphate
US5366648A (en) 1990-02-23 1994-11-22 The Lubrizol Corporation Functional fluids useful at high temperatures
US5068487A (en) 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
US5084197A (en) 1990-09-21 1992-01-28 The Lubrizol Corporation Antiemulsion/antifoam agent for use in oils
EP0524783A1 (de) 1991-07-23 1993-01-27 Oceanfloor Limited Verwendung von Schmierölzusammensetzungen
GB9216014D0 (en) 1992-07-28 1992-09-09 British Petroleum Co Plc Lubricating oils
JP3352123B2 (ja) 1992-10-16 2002-12-03 出光興産株式会社 潤滑油組成物
JP2919206B2 (ja) 1992-11-27 1999-07-12 住友軽金属工業株式会社 アルミニウム及びアルミニウム合金の冷間圧延油及びそれを用いる冷間圧延方法
US5599100A (en) 1994-10-07 1997-02-04 Mobil Oil Corporation Multi-phase fluids for a hydraulic system
US5746933A (en) 1994-11-07 1998-05-05 Nippon Oil Co., Ltd. Lubricating oil and composition for refrigerating machine, and refrigerating machine
US5693598A (en) 1995-09-19 1997-12-02 The Lubrizol Corporation Low-viscosity lubricating oil and functional fluid compositions
AU719520B2 (en) 1995-09-19 2000-05-11 Lubrizol Corporation, The Additive compositions for lubricants and functional fluids
US5824627A (en) 1996-12-13 1998-10-20 Exxon Research And Engineering Company Heterometallic lube oil additives
WO1998026030A1 (en) 1996-12-13 1998-06-18 Exxon Research And Engineering Company Lubricating oil compositions containing organic molybdenum complexes
US6232276B1 (en) 1996-12-13 2001-05-15 Infineum Usa L.P. Trinuclear molybdenum multifunctional additive for lubricating oils
US6010987A (en) 1996-12-13 2000-01-04 Exxon Research And Engineering Co. Enhancement of frictional retention properties in a lubricating composition containing a molybdenum sulfide additive in low concentration
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
CN1105165C (zh) 1997-11-28 2003-04-09 英菲诺姆美国公司 润滑油组合物
US5837657A (en) 1997-12-02 1998-11-17 Fang; Howard L. Method for reducing viscosity increase in sooted diesel oils
US6110878A (en) 1997-12-12 2000-08-29 Exxon Chemical Patents Inc Lubricant additives
US5906968A (en) 1997-12-12 1999-05-25 Exxon Research & Engineering Company Method of synthesizing Mo3 Sx containing compounds
US6143701A (en) 1998-03-13 2000-11-07 Exxon Chemical Patents Inc. Lubricating oil having improved fuel economy retention properties
GB9813070D0 (en) 1998-06-17 1998-08-19 Exxon Chemical Patents Inc Lubricant compositions
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
GB9822578D0 (en) 1998-10-16 1998-12-09 Castrol Ltd An engine oil
US6087307A (en) 1998-11-17 2000-07-11 Mobil Oil Corporation Polyether fluids miscible with non-polar hydrocarbon lubricants
GB2355466A (en) 1999-10-19 2001-04-25 Exxon Research Engineering Co Lubricant Composition for Diesel Engines
US6734150B2 (en) 2000-02-14 2004-05-11 Exxonmobil Research And Engineering Company Lubricating oil compositions
DE60114687T2 (de) 2000-03-29 2006-08-10 Infineum International Ltd., Abingdon Verfahren zur Herstellung von Schmierstoffadditiven
US6677284B2 (en) 2001-03-15 2004-01-13 The Lubrizol Corporation Lubricant composition for ammonia based refrigerants with good seal performance
US6730638B2 (en) 2002-01-31 2004-05-04 Exxonmobil Research And Engineering Company Low ash, low phosphorus and low sulfur engine oils for internal combustion engines
AU2006270083B2 (en) 2005-07-19 2011-01-20 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
WO2008094812A2 (en) * 2007-01-29 2008-08-07 The Lubrizol Corporation Lubricating compositions comprising capped polyoxyalkylene polyols
US8513478B2 (en) 2007-08-01 2013-08-20 Exxonmobil Chemical Patents Inc. Process to produce polyalphaolefins
US7828862B2 (en) 2007-10-31 2010-11-09 Syn-Tech Fine Chemicals Company Limited Highly effective fuel additives for igniting internal combustion engines, diesel engines and jet propulsion engines
US20100093572A1 (en) 2008-10-07 2010-04-15 Paquette Troy F Food Grade Rotary Screw Compressor Lubricant
US8969271B2 (en) * 2009-07-23 2015-03-03 Dow Global Technologies Llc Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2013003405A1 *

Also Published As

Publication number Publication date
SG193977A1 (en) 2013-11-29
WO2013003405A1 (en) 2013-01-03
SG10201604800QA (en) 2016-08-30

Similar Documents

Publication Publication Date Title
US8586520B2 (en) Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
JP5755251B2 (ja) トラクション係数を低下させることによって大きい低速および中速ガスエンジン用のエンジンオイル組成物の燃料効率を向上させる方法
EP2726582A1 (de) Schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern
US8642523B2 (en) Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8598103B2 (en) Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
WO2006101583A1 (en) Blend comprising group iii and group iv basestocks
CA2631723A1 (en) Lubricant composition with improved solvency
US20140274849A1 (en) Lubricating composition providing high wear resistance
US8748362B2 (en) Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
WO2014099286A1 (en) Method for improving engine fuel efficiency
US20130023455A1 (en) Lubricating Compositions Containing Polyetheramines
EP2726584B1 (de) Verfahren zur verbesserung des stockpunktes von schmiermittelzusammensetzungen mit polyalkylenglykolmonoethern
EP2041251A2 (de) Stabile entschäumerzusammensetzung, welche gtl-fluid und/oder hydroentparaffinierungsprodukte und/oder hydroisomerisiertes/katalytisch entparaffiniertes (und/oder lösungsmittelentparaffiniertes) fluid als verdünnungsmittel enthält
EP3642315A1 (de) Schiffsschmieröle und verfahren zu ihrer herstellung und verwendung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140123

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180319

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20180710