EP3484985B1 - Lubrifiants pour moteurs pour la lutte contre les dépôts de siloxane - Google Patents

Lubrifiants pour moteurs pour la lutte contre les dépôts de siloxane Download PDF

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Publication number
EP3484985B1
EP3484985B1 EP17742901.6A EP17742901A EP3484985B1 EP 3484985 B1 EP3484985 B1 EP 3484985B1 EP 17742901 A EP17742901 A EP 17742901A EP 3484985 B1 EP3484985 B1 EP 3484985B1
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Prior art keywords
dispersant
ppm
phosphite
lubricant composition
detergents
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EP17742901.6A
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German (de)
English (en)
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EP3484985A1 (fr
Inventor
Virginia A. Carrick
William D. Abraham
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Lubrizol Corp
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
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    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/252—Diesel engines
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    • C10N2040/255—Gasoline engines
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the disclosed technology relates to a lubricant for a sump-lubricated internal combustion engine, fueled by natural gas, and more particularly, engines fueled by natural gasses containing high levels of siloxanes and other silicon containing compounds, such as are commonly found in landfill gases.
  • Internal combustion engines may be fueled by a variety of liquid or gaseous fuels, including natural gas. While liquefied natural gas or compressed natural gas may sometimes be used to fuel small engines on vehicles, more typically natural gas is used to power large compression ignited or spark ignited "stationary gas" engines that may be fueled by natural gas supplied directly from a gas wellhead.
  • stationary gas engines One common application for stationary gas engines is at landfills, where the engines may be fueled by gas emanating from decomposition of refuse at the landfill.
  • Landfill gasses tend not to be very clean and often have elevated levels of silicon containing compounds and other corrosive materials.
  • the silicon containing compounds in the landfill gas will form siloxane macromolecules which will deposit on the engine component surfaces leading to increased wear in the cylinders, valve areas and bearings. Over time, this wear reduces engine performance, may cause valve seat recession, may increase oil consumption, and may ultimately necessitate refurbishment of the engine.
  • lubricants are replaced once the silicon concentration in the lubricant approaches 120 to 125 parts per million (ppm).
  • lubricant compositions which are formulated, to chemically cleave siloxane macromolecules into smaller compounds that can be more readily dispersed, thus reducing the formation of deposits and rendering the silicon less detrimental in deposit formation even at lubricant silicon concentrations of 125 ppm and higher.
  • the subject lubricating formulations may be effectively used in siloxane deposit control for longer periods of time at elevated silicon concentrations, thereby facilitating the use of unscrubbed natural and landfill gases and extending the oil change intervals, leading to less engine downtime.
  • the invention provides a method for lubricating a natural gas fueled, sump-lubricated, stationary gas engine comprising supplying to the engine a lubricant composition comprising:
  • each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials that are normally understood to be present in the commercial grade.
  • the lubricant formulations will be employed in engines that are fueled with natural gas and in some preferred embodiments, landfill gas.
  • Landfill gas refers primarily to the source of the gas, namely, gas created by the action of microorganisms within a landfill. Such landfill gas may comprise only about 30 to 80 percent methane.
  • the method of operating the engine comprises operating the engine using as its primary or only fuel natural gas having a concentration of silicon that is in excess of 10 mg/m 3 or 15 mg/m 3 or 20 mg/m 3 or 25 mg/m 3 or 30 mg/m 3 as measured by gas chromatography mass spectrometry.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • natural and synthetic oils oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704 , paragraphs [0054] to [0056].
  • a more detailed description of natural and synthetic lubricating oils is provided in paragraphs [0058] to [0059] respectively of WO2008/147704 .
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes.
  • oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are as follows: Group I: >0.03% sulfur and/or ⁇ 90% saturates and viscosity index 80 to 120; Group II: ⁇ 0.03 % S and ⁇ 90% saturates and VI 80 to 120; Group III: ⁇ 0.03 % S and ⁇ 90 % saturates and VI >120; Group IV: all polyalphaolefins; Group V: all others.
  • Groups I, II and III are mineral oil base stocks.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the compound of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed hereinabove) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
  • the lubricant compositions of the present invention will comprise at least one phosphite compound.
  • the phosphite compound will include at least one phosphite ester, and more usefully in some embodiments, at least one phosphite diester or triester compound.
  • the phosphite compound may comprise phosphorous acid (H 3 PO 3 ).
  • phosphite includes the tautomer(s).
  • phosphite esters may be referred to generally as alkyl phosphites or alkyl hydrogen phosphites and these terms may be used interchangeably.
  • Suitable phosphite compounds may include compounds having the general Formula I (R 1 O) 3 P FORMULA I
  • each R 1 independently may be hydrogen or a hydrocarbyl group having 1 to 36, or 1 to 24, or 1 to 18 or 2 to 30 or 2 to 24 or 2 to 10 carbon atoms or 12 to 36 or 12 to 30 or 12 to 20 carbon atoms.
  • the hydrocarbyl group may be a linear or branched, may be a substituted or unsubstituted, may be aromatic or aliphatic or alicylic or heterocyclic or may be saturated or unsaturated and each R 1 may be the same or different.
  • Exemplary phosphite monoesters may include phosphite monesters comprising C 1 to C 30 hydrocarbyl groups.
  • Exemplary phosphite diesters may include dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dipropyl hydrogen phosphite, dibutyl hydrogen phosphite, diethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauryl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite), diphenyl hydrogen phosphite and the like.
  • phosphite triesters include, for example, triphenyl phosphite, triethyl phosphite, tributyl phosphite, tripropyl phosphite, trioctyl phosphite, tri-iso-octyl phosphite, tris 2-ethylhexyl phosphite, tri-isodecyl phosphite, tris tridecyl phosphite, trioleyl phosphite, etc. and the like.
  • the phosphite ester may comprise a polyphosphite ester, which may be produced as the reaction product, e.g., condensation product, of a monomeric phosphorous acid or an ester thereof with at least two alkylene diols.
  • a polyphosphite ester which may be produced as the reaction product, e.g., condensation product, of a monomeric phosphorous acid or an ester thereof with at least two alkylene diols.
  • Exemplary polyphosphite esters are more fully described in International Publication WO2016/089565 .
  • the phosphite compound may comprise a mixture of two or more phosphite compounds.
  • the phosphite compound may comprise a first alkyl phosphite ester having C2 to C10 hydrocarbyl groups and a second alkyl phosphite ester having C12 to C30 hydrocarbyl groups.
  • the phosphite may comprise a mixture of two or more phosphite diesters, wherein one diester has C2 to C10 hydrocarbyl groups and a second diester has C12 to C30 hydrocarbyl groups.
  • the ratio of the C2 to C10 diester to the C12 to C30 diester may be from 20:80 to 80:20 or 40:60 to 60:40 or 60:40 to 90:10.
  • the phosphite may comprise dibutyl phosphite.
  • the phosphite compound may be present in the lubricating composition (on an oil free basis) in an amount from about 0.03 to about 3.0 weight percent with respect to the lubricant composition (or 0.05 to 2.8 wt. % or 0.05 to 2.5 wt. % or 0.1 to 2.5 wt. % or 0.5 to 2.5 wt. % or 1.0 to 2.5 wt. %).
  • the phosphite compounds may be present in an amount to provide 0.001 wt. % to 0.05 wt. % phosphorus (or 10 to 500 ppm phosphorus), or 0.005 to 0.04 wt. % phosphorus, or 0.005 to about 0.03 wt. % phosphorus to the lubricant composition.
  • the phosphite may contribute greater than 80 % or 90% or 95% of the total phosphorous in the lubricant composition.
  • the phosphite compound may constitute the only phosphorous containing antiwear additive in the lubricating composition.
  • the lubricant composition may be free of or substantially free of other phosphorus containing antiwear compounds or other phosphorous containing compounds. In some embodiments, the total amount of phosphorus in the lubricant composition may be less than about 0.03 wt. %
  • Dispersants are well known in the field of lubricants and include what are known as ashless-type dispersants and polymeric dispersants.
  • Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • Typical ashless dispersants include nitrogen-containing dispersants such as N-substituted long chain alkenyl succinimides, also known as succinimide dispersants.
  • the present invention includes at least a first dispersant, wherein the first dispersant is a polyisobutylene succinimide dispersant derived from an ethylene polyamine and having a carbonyl to nitrogen ratio equal or greater than 1 or 1:1 to 4:3 or 1.1:1 to 4:3; at least a second dispersant, wherein the second dispersant comprises a succinimide dispersant having a carbonyl to nitrogen ratio less than 1; and at least a third dispersant, wherein the third dispersant is a polyolefin succinic acid ester dispersant.
  • the first dispersant is a polyisobutylene succinimide dispersant derived from an ethylene polyamine and having a carbonyl to nitrogen ratio equal or greater than 1 or 1:1 to 4:3 or 1.1:1 to 4:3
  • the second dispersant comprises a succinimide dispersant having a carbonyl to nitrogen ratio less than 1
  • at least a third dispersant wherein the third dis
  • the succinimide dispersant may be derived from an aliphatic amine, aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may include such compounds as ethylene polyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
  • Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892 .
  • the dispersant may comprise the condensation product of a hydrocarbyl-substituted succinic anhydride or reactive equivalent thereof with an alkylene polyamine, wherein the alkylene polyamine is a condensed amine.
  • Such dispersants derived from condensed amines are more fully described in US Pat. Pub. 2009/0018040 .
  • the succinimide dispersant may be a derivative of an aromatic amine, an aromatic polyamine, or mixtures thereof.
  • the aromatic amine may be 4-aminodiphenylamine (ADPA) (also known as N- phenylphenylenediamine), derivatives of ADPA, a nitroaniline, an aminocarbazole, an amino-indazolinone, an aminopyrimidine, 4-(4- nitrophenylazo)aniline, or combinations thereof.
  • the dispersant may comprise a derivative of an aromatic amine wherein the aromatic amine has at least three non-continuous aromatic rings.
  • the succinimide dispersant may be a derivative of a polyether amine or polyether polyamine.
  • Typical polyether amine compounds contain at least one ether unit and will be chain terminated with at least one amine moiety.
  • the polyetherpolyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine ® brand and are commercially available from Huntsman Corporation located in Houston, Texas.
  • the polyisobutylene may have a number average molecular weight of 350 to 5000, or 750 to 2500 or 500 to 1500 or 750 to 1250.
  • a succinimide dispersant may be obtained/obtainable from a chlorine-assisted process, often involving Diels-Alder chemistry, leading to formation of carbocyclic linkages from the hydrocarbon chain to the succinic moiety.
  • the process is known to a person skilled in the art.
  • the chlorine-assisted process may produce a dispersant that is a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the non-borated dispersant molecules. Both the thermal and chlorine-assisted processes are described in greater detail in U.S. Patent 7,615,521 , columns 4-5 and preparative examples A and B.
  • a succinimide dispersant may be prepared/ obtained/ obtainable from reaction of succinic anhydride by an "ene” or “thermal” reaction, by what is referred to as a “direct alkylation process.”
  • the "ene” reaction mechanism and general reaction conditions are summarized in " Maleic Anhydride", pages, 147-149, Edited by B.C. Trivedi and B.C. Culbertson and Published by Plenum Press in 1982 .
  • the dispersant prepared by a process that includes an "ene” reaction may be a polyisobutylene succinimide having a carbocyclic ring present of less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the non-borated dispersant molecules.
  • the "ene” reaction may have a reaction temperature of 180°C to less than 300°C, or 200°C to 250°C, or 200°C to 220°C.
  • the polyisobutene particularly useful in preparing an "ene” type succinimide dispersant may desirably have at least 50 percent terminal vinylidene groups, such as at least 60, or 70, or 80 percent.
  • the succinimide dispersant prepared by the "thermal” or “ene” route may be particularly useful.
  • the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents such as boric acid, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the post-treated dispersant may be borated.
  • the post-treated dispersant may be reacted with dimercaptothiadiazoles.
  • the post-treated dispersant may be reacted with phosphoric or phosphorous acid. In one embodiment the post-treated dispersant may be reacted with terephthalic acid and boric acid (as described in US Patent Application US2009/0054278 .
  • the ashless dispersant may be boron-containing, i.e., has incorporated boron and delivers said boron to the lubricant composition.
  • the boron-containing dispersant may be present in an amount to deliver at least 25 ppm boron, or at least 50 ppm boron, or at least 100 ppm or at least 200 ppm or 300ppm or 500 ppm or 200 to 500 ppm or 300 to 500 ppm boron to the lubricant composition.
  • the lubricant composition may be free of a boron- containing dispersant, i.e. the boron containing dispersant delivers no more than 10 ppm boron to the final formulation.
  • the dispersant package comprises three or more dispersants, including at least one polyisobutylene succinimide dispersant derived from an ethylene polyamine and having a carbonyl to nitrogen ratio equal to or greater than 1:1 or between about 1:1 to 4:3 or about 1.1:1 to 4:3 or about 1:1 to about 6:5 or about 1.1:1 to about 6:5, a second dispersant which is a polyisobutylene succinimide dispersant having a carbonyl to nitrogen ratio less than 1:1 and a third dispersant which is an alkenyl (typically polyisobutylene) succinic acid ester dispersant.
  • a second dispersant which is a polyisobut
  • the polyisobutylene succinimide dispersant derived from an ethylene polyamine and having a carbonyl to nitrogen ratio equal to or greater than 1:1 or between about 1:1 to 4:3 or about 1.1:1 to 4:3 or about 1:1 to about 6:5 or about 1.1:1 to about 6:5 will typically comprise from about 5 to 80 wt. % or 10 to 60 wt. %, 15 to 50 wt. % and 15 to 30 wt. % of the total dispersant package.
  • the total dispersant or dispersant package (on an oil free basis) may be present it the lubricant composition in an amount of 1.0 wt % to 6.0 wt. % or 1.5 wt. % to 5.0 wt. %, 2.0 to 4.0 wt. %.
  • the disclosed lubricant may include one or more alkaline or alkali earth metal-containing detergent.
  • the metal-containing detergent which may be present as an additive component in the lubricant is, in one embodiment, an overbased detergent. It may, alternatively, be a neutral detergent.
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound (in this instance, a hydrocarbyl-substituted salicylic acid), a reaction medium comprising at least one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a phenol or alcohol and optionally ammonia.
  • an acidic material typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide
  • a mixture comprising an acidic organic compound (in this instance, a hydrocarbyl-substituted salicylic acid)
  • a reaction medium comprising at least one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for said acidic organic material
  • the acidic organic material will normally have a sufficient number of carbon atoms, for instance, as a hydrocarbyl substituent, to provide a reasonable degree of solubility in oil.
  • the amount of excess metal is commonly expressed in terms of metal ratio.
  • the term "metal ratio" is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • TBN Total Base Number
  • TBN is the amount of strong acid needed to neutralize all of the overbased material's basicity, expressed as potassium hydroxide equivalents (mg KOH per gram of sample). Since overbased detergents are commonly provided in a form which contains a certain amount of diluent oil, for example, 40-50% oil, the actual TBN value for such a detergent will depend on the amount of such diluent oil present, irrespective of the "inherent" basicity of the overbased material. For the purposes of the present invention, the TBN of an overbased detergent is to be recalculated to an oil-free basis.
  • Detergents which are useful in the present invention typically have a TBN (oil-free basis) of 100 to 800, and in one embodiment 150 to 750, and in another, 400 to 700. If multiple detergents are employed, the overall TBN of the detergent component (that is, an average of all the specific detergents together) will typically be in the above ranges.
  • the metal compounds useful in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements).
  • the Group 1 metals of the metal compound include Group 1a alkali metals such as sodium, potassium, and lithium, as well as Group 1b metals such as copper.
  • the Group 1 metals can be sodium, potassium, lithium and copper, and in one embodiment sodium or potassium, and in another embodiment, sodium.
  • the Group 2 metals of the metal base include the Group 2a alkaline earth metals such as magnesium, calcium, and barium, as well as the Group 2b metals such as zinc or cadmium.
  • the Group 2 metals are magnesium, calcium, barium, or zinc, and in another embodiments magnesium or calcium.
  • the metal is magnesium, calcium or sodium or a mixture of calcium and magnesium.
  • the lubricant is zinc free or substantially zinc free and thus will not include zinc containing detergents.
  • the metal compounds are delivered as metal salts.
  • the anionic portion of the salt can be hydroxide, oxide, carbonate, borate, or nitrate.
  • the lubricants may contain an overbased sulfonate detergent.
  • Oil-soluble sulfonates can be represented by one of the following formulas: R 2 -T-(SO 3 ) a and R 3 -(SO 3 -) b , where T is a cyclic nucleus such as typically benzene; R 2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R 2 )-T typically contains a total of at least 15 carbon atoms; and R 3 is an aliphatic hydrocarbyl group typically containing at least 15 carbon atoms.
  • R 3 are alkyl, alkenyl, alkoxyalkyl, and carboalkoxyalkyl groups.
  • the sulfonate detergent may be a predominantly linear alkylbenzenesulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US Patent Application 2005-065045 .
  • the phenols useful in making phenate detergents can be represented by the formula (R 4 ) a -Ar-(OH) b , wherein R 5 is an aliphatic hydrocarbyl group of 4 to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms; Ar is an aromatic group (which can be a benzene group or another aromatic group such as naphthalene); a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
  • a and b are independently numbers in the range of 1 to 4, or 1 to 2.
  • R 4 and a are typically such that there is an average of at least 8 aliphatic carbon atoms provided by the R 4 groups for each phenol compound.
  • Phenate detergents are also sometimes provided as sulfur-bridged species.
  • the phenate detergent contains less than 20% or less than 10% or less than 5% or less than 2% or less than 1%, e.g., 0 or 0.05% to 0.5% of monomeric para-dodecylphenol or sulfurized monomer thereof or salt thereof, based on the active chemical amount of the phenate detergent.
  • detergent may comprise a salicylate detergent such as an overbased calcium hydrocarbyl-substituted salicylate detergent.
  • a salicylate detergent such as an overbased calcium hydrocarbyl-substituted salicylate detergent.
  • the presence of a salicylate detergent may be beneficial in providing oxidation resistance to the lubricant.
  • the salicylate detergent has a Total Base Number of about 200 to about 700 or 250 to 500 or 250 to 400 or 300 to 700 or 450 to 700 or greater than about 400 on an oil free basis, that is, factoring out the effect of diluent oil.
  • Salicylate detergents are known; see, for instance, U.S. Pat. Nos. 5,688,751 or 4,627,928 .
  • the detergent may comprise an overbased calcium salicylate detergent and in another embodiment, an overbased magnesium salicylate detergent and in still another embodiment a mixture of calcium and magnesium salicylate detergents.
  • the overbased material is an overbased saligenin detergent.
  • Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives.
  • Saligenin detergents are disclosed in greater detail in U.S. Patent 6,310,009 , with special reference to their methods of synthesis (Column 8 and Example 1) and suitable amounts of the various species of X and Y (Column 6).
  • Salixarate detergents may also be present. Salixarates and methods of their preparation are described in greater detail in U.S. patent number 6,200,936 and PCT Publication WO 01/56968 . It is believed that the salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
  • Patents describing techniques for making basic salts of sulfonic acids, carboxylic acids, (hydrocarbyl-substituted) phenols, phosphonic acids, and mixtures of any two or more of these include U.S. Patents 2,501,731 ; 2,616,905 ; 2,616,911 ; 2,616,925 ; 2,777,874 ; 3,256,186 ; 3,384,585 ; 3,365,396 ; 3,320,162 ; 3,318,809 ; 3,488,284 ; and 3,629,109 .
  • overbased detergents can include overbased detergents having a Mannich base structure, as disclosed in U.S. Patent 6,569,818 .
  • Either a single detergent or multiple additional detergents can be present.
  • the amount of the detergent or detergents (individually or in total) in the lubricants of the present technology may be 0.5 to 5 percent by weight, or 1 to 3 percent. The amount in a concentrate will be correspondingly higher.
  • the total amount of detergents present in the lubricants of the disclosed technology may be an amount suitable to provide 1 to 5 TBN, or 2 to 4, or 2.5 to 3 TBN to the lubricant.
  • the lubricant compositions of the present invention may comprise a boron containing compound or mixture of boron containing compounds in an amount to provide the lubricant composition with 25 ppm boron, or at least 50 ppm boron, or at least 100 ppm or at least 200 ppm or 300 ppm or 500 ppm or 200 to 500 ppm or 300 to 500 ppm boron to the lubricant composition.
  • Useful boron containing compounds may include boric acid (including metaboric acid, HB0 2 , orthoboric acid, H 3 BO 3 , and a tetraboric acid, H 2 B 4 0 7 ) and borate esters, which may be prepared by the reaction of boric acid, a boric oxide, a boron trioxide or an alkyl borate and at least one compound selected from epoxy compounds, halohydrin compounds, epihalohydrin compounds, alcohols and mixtures thereof.
  • the alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols or higher alcohols.
  • Borate esters may also be prepared from boron halides.
  • the borated ester may contains at least one hydrocarbyl group often containing about 4 to about 30, or 8 to about 30 carbon atoms.
  • the boron containing compound may comprise a borate ester comprising at least one C8 to C30 hydrocarbyl group.
  • the boron containing compound may comprise one or more borated dispersants discussed above. In one embodiment, it the boron containing compound may comprise a mixture of a borate ester and a boron containing dispersant.
  • the lubricant of the disclosed technology may also contain 3 to 80 ppm (or 5 to 70, or 10 to 60, or 20 to 50 ppm) of one or more silicon-containing antifoam agents. At least a small amount of such an antifoam agent is desirable to minimize foaming while the lubricant is lubricating the engine. However, an excessive amount may be deleterious to the anti-emulsion performance of the lubricant as it may be used for the lubrication of a compressor.
  • Silicon antifoam agents may be fluorinated molecules, or molecules without fluorine, or mixtures of such molecules. Such materials are commercially available and includes such species as polydimethylsiloxane and trimethyl, trifluoropropylmethyl siloxane. These materials may be provided commercially as oil-diluted compositions; the amounts reported herein are an oil-free basis.
  • the disclosed lubricant may also contain a silicon-free polymeric antifoam agent.
  • the amount of this agent if it is present, may be up to 200 parts per million by weight, e.g., 10 to 200, or 20 to 100, or 25 to 80, or 30 to 70 ppm.
  • the silicon-free polymeric antifoam agent may comprise an alkyl acrylate polymer, such as a copolymer of ethyl acrylate and 2-ethylhexyl acrylate. Such an antifoam agent may aid in improving anti-emulsion performance of the lubricant.
  • Corrosion inhibitors typically may include nitrogen-containing materials such as triazoles and thiadiazoles and derivatives thereof. Suitable triazoles include aromatic triazoles such as benzotriazole or alkylbenzotriazoles such as tolutriazole.
  • Thiadiazoles include dimercaptothiadiazoles and mono- or di-alkyl derivatives of dimercaptothiadiazoles. (including species with multiple S atoms in a chain).
  • the amount of the corrosion inhibitor (such as the amount of the aromatic triazole) may be 0.001 to 0.1 wt. %, or 0.003 to 0.03 wt. %, or 0.005 to 0.1 wt. %.
  • crankcase lubricants may typically contain any or all of the following components hereinafter described.
  • Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group or a group bridging two aromatic rings. They may also contain an ester group at the para position, for example, an antioxidant of the formula wherein R 3 is a hydrocarbyl group such as an alkyl group containing, e.g., 1 to 18 or 2 to 12 or 2 to 8 or 2 to 6 carbon atoms; and t-alkyl can be t-butyl.
  • antioxidants are described in greater detail in U.S. Patent 6,559,105 .
  • Antioxidants also include aromatic amines, such as nonylated diphenylamines.
  • Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds.
  • U.S. Pat. No. 4,285,822 discloses lubricating oil compositions containing a molybdenum and sulfur containing composition. Typical amounts of antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5 wt. % or 0.15 to 4.5 wt. % or 0.2 to 4 wt. %. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
  • Viscosity improvers may be included in the disclosed compositions. Viscosity improvers are usually polymers, including polyisobutenes, polymethacrylic acid esters, diene polymers, polyalkylstyrenes, esterified styrenemaleic anhydride copolymers, alkenylarene-conjugated diene copolymers and polyolefins. Multifunctional viscosity improvers, which also have dispersant and/or antioxidancy properties are known and may optionally be used. Viscosity improvers may be used at, e.g., 0.1 to 0.8 wt. % or 0.3 to 0.6 wt. %.
  • the lubricant compositions of the present invention may include one or more antiwear agents other than the phosphite compounds disclosed above.
  • anti-wear agents may include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, and phosphorus-containing carboxylic acids, esters, ethers, and amides.
  • the present technology is particularly useful for formulations in which the total amount of phosphorus as delivered by various components including the antiwear agent, does not exceed 0.075% or 0.07% or 0.06%. Suitable amounts may include 0.005 to about 0.055 percent by weight or 0.01 to 0.05 percent or 0.02 to 0.05 percent.
  • Non-phosphorus-containing anti-wear agents which may also be used, include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
  • additives that may optionally be used in lubricating oils include pour point depressing agents, extreme pressure agents, and color stabilizers.
  • the present technology is particularly useful also when the total sulfated ash of a lubricant is relatively low, for instance, less than 1 % or less than 0.8%, e.g., 0.01 to 0.8, or 0.1 to 0.75, or 0.2 to 0.7 %.
  • a lubricant formulation may be free or substantially free of any zinc containing compounds, such as the antiwear agent zinc dialkyldithiophosphate (ZDDP).
  • ZDDP zinc dialkyldithiophosphate
  • the lubricant may be free of or substantially free of any metal thiophosphates.
  • the lubricant formulations of the present invention are intended to effectively inhibit siloxane deposit formation and associated engine wear in engines fueled using natural or landfill gas having high concentrations of silicon, while also maintaining or improving seals performance and corrosion inhibition.
  • the lubricant composition may comprise greater than 120 ppm or 125 ppm or 130 ppm or 140 or 160 or 175 or 200 or 250 or 300 ppm of silicon. This silicon may be derived from contamination from silicon compounds in the fuel source or byproducts of combustion of the fuel source.
  • a low-ash stationary-gas engine lubricant may be prepared comprising an oil of lubricating viscosity, 2.54 wt. % of a succinimide dispersant (chlorine-route); 0.74 wt. % of overbased Ca sulfonate detergent(s); 0.97 wt. % overbased Ca phenate detergent(s), 0.27 wt. % zinc dialkylthiophosphate(s); 2.85 wt. % antioxidants (phenolic, aminic, and/or sulfurized olefin); 0.35 wt. % of a borate ester, and 0.007 percent by weight of polydimethylsiloxane antifoam agent (commercial material, about 10% in oil, corresponding to 7 ppm antifoam agent on an active chemical basis).
  • a succinimide dispersant chlorine-route
  • 0.74 wt. % of overbased Ca sulfonate detergent(s) 0.97 wt. %
  • a low-ash stationary-gas engine lubricant may be prepared comprising an oil of lubricating viscosity, 0.24 wt. % of a phosphite compound(s), 1.8 wt. % of a succinimide dispersant (chlorine-route); 0.6 wt. % of a polyisobutylene succinimide dispersant with a carbonyl to nitrogen ratio of 4:3, 0.34 wt.% of a borated succinimide dispersant, 0.28 wt. % succinic acid ester dispersant, 0.1 wt. % of a polypropylene oxide, 1.2 wt.
  • % of overbased Ca salicylate detergent 2.95 wt. % antioxidants (phenolic, aminic, and/or sulfurized olefin); 0.35 wt. % of a borate ester, 0.01 wt. % of a corrosion inhibitor, 0.05 wt. % of a titanium alkylate and 0.007 percent by weight of polydimethylsiloxane antifoam agent (commercial material, about 10% in oil, corresponding to 7 ppm antifoam agent on an active chemical basis).
  • antioxidants phenolic, aminic, and/or sulfurized olefin
  • 0.35 wt. % of a borate ester 0.01 wt. % of a corrosion inhibitor, 0.05 wt. % of a titanium alkylate and 0.007 percent by weight of polydimethylsiloxane antifoam agent (commercial material, about 10% in oil, corresponding to 7 ppm antifoam agent on an active chemical basis).
  • the term "substantially free of” means that the material in question is only present in amounts consistent with contamination and/or by-products present in commercial grades of desired components.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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Claims (13)

  1. Procédé de lubrification d'un moteur stationnaire à gaz alimenté en gaz naturel, lubrifié par carter d'huile, comprenant l'administration d'une composition lubrifiante au moteur comprenant :
    (a) une huile de viscosité lubrifiante ;
    (b) 0,03 à 3,0 % en poids par rapport à la composition lubrifiante (ou 0,05 à 2,8 % en poids ou 0,05 à 2,5 % en poids) d'un composé de phosphite ;
    (c) un détergent contenant du métal ;
    (d) au moins un premier dispersant, dans lequel le premier dispersant est un dispersant à base de succinimide de polyisobutylène dérivé d'une polyamine d'éthylène et ayant un rapport carbonyle/azote égal ou supérieur à 1 ou 1:1 à 4:3 ou 1,1:1 à 4:3 ;
    (e) au moins un deuxième dispersant, le deuxième dispersant comprenant un dispersant à base de succinimide ayant un rapport carbonyle/azote inférieur à 1 ; et
    (f) au moins un troisième dispersant, le troisième dispersant étant un dispersant à base de polyoléfine d'ester d'acide succinique ;
    (g) un composé contenant du bore en quantité suffisante pour fournir au moins 25 ppm (ou au moins 50 ppm, ou 100 ppm, ou 200 ppm ou 300 ppm ou 500 ppm) de bore à la composition lubrifiante ;
    la composition lubrifiante étant exempte ou sensiblement exempte de zinc, et
    la composition lubrifiante ayant une teneur en cendres sulfatées inférieure à 1,0 % en poids (ou 0,7 % en poids).
  2. Procédé selon la revendication 1, dans lequel le composé de phosphite comprend un diester de phosphite ayant des groupes ester de 2 à 10 atomes de carbone et un diester de phosphite ayant des groupes ester de 12 à 30 atomes de carbone.
  3. Procédé selon la revendication 1 ou 2, dans lequel les composés de phosphite comprennent du phosphite de dibutyle.
  4. Procédé selon les revendications 1 à 3, dans lequel le composé de phosphite fournit 0,001 % en poids à 0,05 % en poids de phosphore (ou 10 à 500 ppm de phosphore), ou 0,005 à 0,04 % en poids de phosphore, ou 0,005 à 0,03 % en poids à la composition lubrifiante.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le premier dispersant est présent en une quantité de 0,1 % en poids à 2 % en poids (ou de 0,1 à 1,5 % en poids, ou de 0,2 % en poids à 2 % en poids ou de 0,3 % en poids à 1 % en poids) de la composition lubrifiante.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le détergent contenant du métal est choisi dans le groupe constitué par les détergents à base de phénate, les détergents à base de sulfonate, les détergents à base de salicylate, les détergents à base de salixarate, les détergents à base de saligénine et leurs mélanges.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le détergent contenant du métal comprend un détergent à base de salicylate.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel le métal du détergent contenant du métal est choisi dans le groupe constitué par le magnésium et le calcium et leurs mélanges.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel la composition lubrifiante a une concentration en silicium supérieure à 125 ppm (ou 130 ppm ou 140 ppm).
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel le moteur est alimenté en gaz naturel ayant une concentration en silicium supérieure à 10 mg/m3 (ou 15 mg/m3 ou 20 mg/m3 ou 25 mg/m3 ou 30 mg/m3) telle que mesurée par spectrométrie de masse par chromatographie en phase gazeuse.
  11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le composé contenant du bore comprend un ester de borate ayant au moins un groupe hydrocarbyle de 8 à 30 atomes de carbone.
  12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel le composé contenant du bore comprend un dispersant boré.
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition lubrifiante a 50 à 500 ppm (ou 50 à 300 ppm) de phosphore.
EP17742901.6A 2016-07-15 2017-07-10 Lubrifiants pour moteurs pour la lutte contre les dépôts de siloxane Active EP3484985B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662362665P 2016-07-15 2016-07-15
PCT/US2017/041308 WO2018013451A1 (fr) 2016-07-15 2017-07-10 Lubrifiants pour moteurs pour la lutte contre les dépôts de siloxane

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EP3484985B1 true EP3484985B1 (fr) 2022-06-08

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US (1) US20190292484A1 (fr)
EP (1) EP3484985B1 (fr)
CN (1) CN109715770B (fr)
CA (1) CA3030950A1 (fr)
PL (1) PL3484985T3 (fr)
WO (1) WO2018013451A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3655509B1 (fr) * 2017-07-17 2022-12-07 The Lubrizol Corporation Composition de lubrifiant à faible teneur en zinc
CN116695125B (zh) * 2023-05-15 2023-11-21 无锡中石油润滑脂有限责任公司 一种防锈型轴承润滑脂清洗剂组合物及其制备方法与应用

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Also Published As

Publication number Publication date
WO2018013451A1 (fr) 2018-01-18
PL3484985T3 (pl) 2022-09-19
CN109715770B (zh) 2023-05-26
CN109715770A (zh) 2019-05-03
EP3484985A1 (fr) 2019-05-22
US20190292484A1 (en) 2019-09-26
CA3030950A1 (fr) 2018-01-18

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