EP3512927B1 - Composition lubrifiante comprenant un détergent à base de sulfonate et un composé phénolique d'hydrocarbyle exempt de cendres - Google Patents

Composition lubrifiante comprenant un détergent à base de sulfonate et un composé phénolique d'hydrocarbyle exempt de cendres Download PDF

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Publication number
EP3512927B1
EP3512927B1 EP17772255.0A EP17772255A EP3512927B1 EP 3512927 B1 EP3512927 B1 EP 3512927B1 EP 17772255 A EP17772255 A EP 17772255A EP 3512927 B1 EP3512927 B1 EP 3512927B1
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Prior art keywords
lubricating composition
group
hydrocarbyl
carbon atoms
oxyalkylated
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EP17772255.0A
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German (de)
English (en)
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EP3512927A1 (fr
Inventor
Yanshi Zhang
Ewan DELBRIDGE
Mary Galic Raguz
Alexandra Mayhew
Thomas Derevjanik
John LOOP
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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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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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
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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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
    • C10M2207/027—Neutral salts thereof
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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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
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    • 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
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    • 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
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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
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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
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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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
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
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    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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    • 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
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/28—Amides; Imides
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • 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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    • 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
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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
    • C10N2030/04—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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
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    • 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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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
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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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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • the disclosed technology provides lubricating compositions comprising an oil of lubricating viscosity, an alkaline earth metal sulfonate detergent having a metal ratio of at least 10, in an amount to contribute 3 to 14 g KOH/kg of TBN to the lubricating composition, an ashless, sulfur free, hydrocarbyl phenolic compound in an amount of 0.4 to about 6.0 weight percent (wt%) of the composition, and an ashless dispersant; wherein the lubricating composition has total ash of 0.3 to 1.8 wt%, total detergent soap of 0.1 to 1.2 wt% and wherein the lubricating composition contains less than 0.1 wt% of a sulfur-containing phenolic detergent.
  • the disclosed technology further relates to a method of lubricating an internal combustion engine with the lubricating composition.
  • the disclosed technology further relates to the use of the of the lubricating composition in an internal combustion engine to improve control of at least one of the following: (i) fuel economy, (ii) corrosion, (iii) cleanliness, (iv) bore wear and (v) seals protection.
  • Lubricating compositions for heavy duty diesel engines have historically relied on sulfonate and particularly high soap containing sulfonate detergents for cleanliness.
  • high soap refers to a detergent having a metal ratio of less than 5.
  • High soap sulfonates contribute heavily to ash and little to lubricant total base number (TBN) and thus, there is a desire to formulate away from the use of high soap sulfonate detergents, while maintaining lubricant properties, such as cleanliness and seals performance.
  • TBN total base number
  • One potential alternative is to replace high soap sulfonates with phenate detergents, which contributed TBN and lower ash; however, regulatory pressure is reducing the desirability of formulating with phenate detergents.
  • the objectives of the disclosed technology include providing a lubricating composition which results in acceptable or improved control of at least one of the following (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness, (iv) control of bore wear, and (v) seals protection in an internal combustion engine, which may be a heavy duty diesel internal combustion engine.
  • the disclosed technology provides a lubricating composition
  • a lubricating composition comprising: an oil of lubricating viscosity, an alkaline earth metal sulfonate detergent having a metal ratio of at least 10, in an amount to contribute 3 to 14 g KOH/kg of TBN to the lubricating composition, an ashless, sulfur-free, hydrocarbyl phenolic compound in an amount 0.4 wt% to about 6.0 wt% of the composition and wherein the lubricating composition has total ash of 0.3 to 1.8 wt%, total detergent soap of 0.1 to 0.9 wt% and wherein the lubricating composition contains less than 0.1 wt% of a sulfur-containing phenolic detergent.
  • the ashless, sulfur free phenolic compound comprises an oxyalkylated hydrocarbyl phenolic compound.
  • the lubricating composition comprises less than 0.1 wt% of an alkaline earth metal sulfonate deteregent having a metal ratio of less than 10.
  • the lubricating composition may comprise less than 0.3 wt% or 0.2 wt% or 0.1 wt% or 0.05 wt% or 0.01 wt% of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 and in another embodiment, may be free or substantially free of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10.
  • the ashless, sulfur free, hydrocarbyl phenolic compound may comprise an oxyalkylated hydrocarbyl phenolic compound.
  • the oxyalkylated hydrocarbyl phenolic compound may comprise a hydrocarbyl group containing 25 to 200 carbon atoms or 25 to 175 or 25 to 140, or 30 to 100 carbon atoms.
  • the oxyalkylated hydrocarbyl phenolic compound may comprise an oxyalkylated polyisobutylene phenolic compound.
  • the oxyalkylated group of the oxyalkylated hydrocarbyl phenolic compound may have the formula -(R 1 O) n -, wherein each R 1 is independently selected from the group consisting of an ethylene group, a propylene group, and a butylene group; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5.
  • the oxyalkylated hydrocarbyl phenolic compound may be present in an amount of 0.4 wt% to about 5.0 wt% (or 0.4 to 4.0 wt%, or 0.5 to 2.5 wt% or 0.7 to 2.0 wt%) of the lubricating composition.
  • the ashless, sulfur free, hydrocarbyl phenolic compound may comprise an oxyalkylated hydrocarbyl phenolic compound and an alkylated phenolic antioxidant (selected from alkyl phenols, hindered phenols, coupled phenolic compounds and mixtures).
  • the alkylated phenolic antioxidant may be derived from a 2,6 dialkyl phenol, wherein each alkyl group is independently selected from alkyl groups containing 3 to 8 carbon atoms.
  • the alkylated phenolic antioxidant may be present in an amount of at least 0.1 wt%, or 0.2 wt% or 0.5 wt% and up to about 3.0 wt% or 2.5 wt% or 2.0 wt% or 1.5 wt%.
  • the ashless dispersant may comprise the reaction product of a high-vinylidene polyisobutylene acylating agent and an amine, wherein the polyisobutylene contains greater than about 50 mole%, 60 mole%, or 70 mole% or greater and usually about 80 mole% or greater or 90 mole% or greater of alpha-vinylidene and/or beta- double bond isomer.
  • the metal of the alkaline earth metal sulfonate detergent may be selected from calcium, magnesium, and titanium.
  • the lubricating composition may further comprise a boron containing compound.
  • the lubricating composition may be substantially free of phenates.
  • the lubricating composition may have a total TBN of 3 to 15 gKOH/Kg.
  • the lubricating composition may have a phosphorus level between about 0.04 and about 0.12 wt%.
  • the disclosed technology provides a method of lubricating an internal combustion engine comprising supplying to the internal combustion engine a lubricating composition of a lubricating disclosed herein.
  • the engine may be a compression-ignition internal combustion engine, which may be a heavy duty diesel internal combustion engine.
  • the vehicle powered by the compression-ignition internal combustion engine may have a maximum laden mass over 3,500 kg.
  • the lubricating composition may have a SAE viscosity grade of XW-Y, wherein X may be 0, 5, 10, or 15; and Y may be 16, 20, 30 or 40.
  • the internal combustion engine may have a steel surface on a cylinder bore, a cylinder block, and/or a piston ring.
  • the disclosed technology may also provide for a method of providing high TBN lubricant composition while maintaining good cleanliness and/or corrosion control in a compression-ignition internal combustion engine comprising supplying to the engine a lubricating composition disclosed herein.
  • the disclosed technology provides for the use of the lubricating composition described herein to provide at least one of (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness (typically control of deposits, typically control/reduction of soot), (iv) control of bore wear and (v) control of seals wear in an internal combustion engine.
  • the internal combustion engine is a heavy duty diesel internal combustion engine.
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of” and “consisting of,” where “consisting of” excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel, and essential characteristics of the composition or method under consideration.
  • TBN total base number as measured using ASTM D2986-11.
  • hydrocarbyl As used herein, the term "hydrocarbyl”, “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 disclosed technology, 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.
  • hydrocarbyl substituent or “hydrocarbyl group” is described in paragraphs [0118] to [0119] of PCT Publication WO2008/147704 , or a similar definition in paragraphs [0137] to [0141] of US Publication 2010-0197536 .
  • detergent soap means the neutral metal salt of the detergent substrate, where the term “substrate” means the anionic component of the soap.
  • the term “free of” may mean that none of the substance is intentionally added or that the amount present is not detectable by common methods or is not detectable at greater than contaminant amounts. "Substantially free of” means that the material is present in an amount less than that amount which will have a commercially useful benefit for the property contributed by the additive in question.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • PCT Publication WO2008/147704 paragraphs [0054] to [0056] (a similar disclosure is provided in US Publication 2010/197536 , see [0072] to [0073]).
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment 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 defined as specified in April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3, sub-heading 1.3. "Base Stock Categories.”
  • the API Guidelines are also summarised in US Patent 7,285,516 (see column 11, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group II, Group III, Group IV oil, or mixtures thereof.
  • 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 disclosed technology 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 disclosed technology (comprising the additives disclosed herein) 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 lubricating compositions may comprise one or more detergents, including at least one alkaline earth metal sulfonate detergent having a metal ratio of at least 10.
  • the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 will be present in the lubricating composition in an amount to contribute between about 3 to 14 g KOH/kg of TBN, or about 5 to 12 g KOH/kg of TBN to the lubricating composition. For purposes of clarity, this refers to the sum of the TBN contributed by all of the alkaline earth metal sulfonate detergents having a metal ratio of at least 10 that are in the lubricating composition.
  • the lubricating composition will also have a total amount of detergent soap, that is, the sum of all soap from all detergents, of 0.1 to 1.2 wt% or 0.1 to 1.1 wt% or 0.1 to 0.9 wt% (or 0.3 to 0.9 wt% or 0.5 to 0.9 wt%) with respect to the lubricating composition.
  • Suitable alkaline earth metal sulfonate detergents may include magnesium or calcium sulfonate detergents and mixtures thereof.
  • the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may be a calcium sulfonate detergent and in another embodiment, may be a magnesium sulfonate detergent and in still another embodiment may comprise a mixture of a magnesium and calcium sulfonate detergent, each having a metal ratio of at least 10.
  • metal ratio means 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.
  • metal ratio is also explained in standard textbook entitled “ Chemistry and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219 , sub-heading 7.25.
  • the alkaline earth metal sulfonate detergent will have a metal ratio of 10 and higher or 12 or 14 or 16 or 20 and higher.
  • the metal ratio may be 10 to about 30.
  • the alkaline earth metal sulfonate detergent may be overbased.
  • Overbased detergents are known in the art.
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally single phase, 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, typically carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a calcium chloride, acetic acid, phenol or alcohol.
  • the acidic organic material will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
  • the alkaline earth metal sulfonate detergent having a metal ratio of 10 or higher may typically have a total base number of 250 to 600, or 300 to 500.
  • the alkaline earth metal sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 10.
  • Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof.
  • the predominantly linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • the sulfonate detergent may be a branched alkylbenzene sulfonate detergent.
  • Branched alkylbenzene sulfonate may be prepared from isomerized alpha olefins, oligomers of low molecular weight olefins, or combinations thereof. Typically oligomers include tetramers, pentamers, and hexamers of propylene and butylene.
  • the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds.
  • the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may be present at 0.2 wt% to 2.5 wt%, or 0.3 wt% to 2.2 wt%, or 0.6 wt% to 1.8 wt%.
  • the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may comprise a magnesium sulfonate detergent and a calcium sulfonate detergent.
  • the lubricating compositions of the present invention will comprise less than 0.3 wt% or less than 0.2 wt% or less than 0.1 wt% of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 (or 5) and another embodiment, may be free of or substantially free of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 (or less than 5).
  • the lubricating composition of the present invention may comprise one or more additional detergents, other than the alkaline earth metal sulfonates discussed above, provided the total soap from all detergents does not exceed the limit of 1.2 wt% or 1.1 wt% or 0.9 wt% of the lubricating composition.
  • phenol-based detergents may be present and may be chosen from a non-sulfur containing phenate, a sulfur- coupled phenate, a salixarate, a salicylate, a saligenin, and mixtures thereof.
  • Non-sulfur containing phenates and sulfur containing phenates are known in the art.
  • the non-sulfur containing phenate, or sulfur containing phenate may be neutral or overbased.
  • an overbased non-sulfur containing phenate, or a sulfur containing phenate will have a total base number of 180 to 450 TBN and a metal ratio of 2 to 15, or 3 to 10.
  • a neutral non-sulfur containing phenate, or sulfur containing phenate may have a TBN of 50 to less than 180 and a metal ratio of 1 to less than 2, or 0.05 to less than 2.
  • Phenate detergents are typically derived from p-hydrocarbyl phenols. Alkylphenols of this type may be coupled with sulfur and overbased, coupled with aldehyde and overbased, or carboxylated to form salicylate detergents. For purposes of clarity, a carboxylated phenate detergent is referred to herein as a salicylate detergent and not a phenate detergent and thus is not included in phenate detergents for purposes of embodiments containing restrictions on the amount of phenate detergent present.
  • Suitable alkylphenols include those alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e.
  • Suitable alkylphenols also include those alkylated with oligomers of butane, especially tetramers and pentamers of n-butenes.
  • Other suitable alkylphenols include those alkylated with alpha-olefins, isomerized alpha-olefins, and polyolefins like polyisobutylene.
  • the lubricating composition may comprise a neutral non-sulfur containing phenate, or sulfur containing phenate having a TBN of 50 to less than 180 or 50 to 150 or 50 to 100 and a metal ratio of 1 to less than 2, or 0.05 to less than 2.
  • the non-sulfur containing phenate, or sulfur containing phenate may be in the form of a calcium or magnesium non-sulfur containing phenate, or sulfur containing phenate (typically calcium non-sulfur containing phenate, or sulfur containing phenate).
  • the lubricating composition may comprise 0.1 to 0.9 wt%, or 0.2 to 0.9 wt% or 0.5 to 0.9 wt% or 0.6 to 0.8 wt% of a sulfur free phenate detergent, which may be a formaldehyde (methylene) coupled magnesium or calcium phenate detergent, typically a magnesium phenate detergent, which may be neutral or overbased and is typically neutral.
  • a sulfur free phenate detergent which may be a formaldehyde (methylene) coupled magnesium or calcium phenate detergent, typically a magnesium phenate detergent, which may be neutral or overbased and is typically neutral.
  • the lubricating composition may comprise less than 0.1 wt%, or less than 0.05 wt%, or even less than 0.01 wt% of a sulfur containing phenate detergent. In one embodiment, the lubricating composition is free or substantially free of a sulfur containing phenate detergent.
  • the lubricating composition may comprise less than 0.1 wt%, or less than 0.05 wt%, or even less than 0.01 wt% of any phenate detergent.
  • the lubricating composition may be free of an overbased phenate, and in a different embodiment the lubricating composition may be free of a non-overbased phenate.
  • the lubricating composition may be free of a metal containing phenate detergent.
  • the lubricating composition may be free of an ashless containing phenate detergent.
  • the lubricating composition may comprise a metal containing salicylate detergent that may be neutral or overbased.
  • Salicylate detergents are known in the art.
  • the salicylate detergent may have a TBN of 50 to 400, or 150 to 350, and a metal ratio of 0.5 to 10, or 0.6 to 2.
  • Suitable metal containing salicylate detergents may include derivates of alkylated salicylic acid, or alkylsalicylic acid.
  • Alkylsalicylic acid may be prepared by alkylation of salicylic acid or by carbonylation of alkylphenol. When alkylsalicylic acid is prepared from alkylphenol, the alkylphenol is selected in a similar manner as the phenates described above.
  • alkylsalicylate of the invention include those alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e. p- dodecylphenol or PDDP) and pentapropenylphenol.
  • Suitable alkylphenols also include those alkylated with oligomers of butane, especially tetramers and pentamers of n-butenes.
  • Other suitable alkylphenols include those alkylated with alpha-olefins, isomerized alpha-olefins, and polyolefins like polyisobutylene.
  • the lubricating composition comprises a calcium salicylate detergent, a magnesium salicylate detergent or mixtures thereof, typically a calcium salicylate detergent.
  • the metal containing salicylate detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.
  • the lubricating composition may comprise a metal containing salixarate detergent that may be neutral or overbased.
  • Salixarate derivatives and methods of their preparation are described in greater detail in U.S. Patent 6,200,936 and PCT Publications WO01/56968 and WO03/18728 . 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.” Additionally Linear” does not exclude branching or other structures in the substituent R groups.
  • the salixarate may have a TBN of 50 to 300, or 100 to 260 and a metal ratio of 1 to 10, or 2 to 6.5.
  • the metal containing salixarate detergent may be present 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.
  • the lubricating composition may comprise a metal containing saligenin detergent.
  • the saligenin may be a calcium or magnesium (typically magnesium) detergent.
  • Saligenin derivatives and methods of their preparation are described in greater detail inter alia U.S. Patent 6,310,009 .
  • the metal containing saligenin detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.
  • the lubricating composition may comprise a metal containing carboxylate detergent.
  • the carboxylate may be a calcium or magnesium (typically magnesium) detergent.
  • the metal containing carboxylate detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.
  • the metal-containing phenol detergents may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 and 6,281,179 .
  • phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 and 6,281,179 .
  • hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
  • the metal cation of the metal containing detergents may be from an alkaline earth metal such as calcium, barium or magnesium, or an alkali metal such as sodium, or potassium.
  • the lubricating compositions of the present invention further comprises an ashless, sulfur free, hydrocarbyl phenolic compound in an amount from 0.4 to about 6.0 wt%, or 1.0 to 6.0 wt% or 1.0 to 5.0 wt% or 1.5 to 5.0 wt% or 1.5 to 4.0 wt% or 1.5 to 3.0 wt% of the lubricating composition.
  • the ashless sulfur free hydrocarbyl compound comprises an oxyalkylated hydrocarbyl phenolic compound.
  • the oxyalkylated hydrocarbyl phenolic compound may be represented by the formula: wherein
  • the oxyalkylated hydrocarbyl phenol may be represented by the formula: wherein
  • the oxyalkylated hydrocarbyl phenol may be represented by the formula: wherein
  • the oxyalkylated hydrocarbyl phenol may be represented by the formula: wherein
  • the R 4 group of each of the formulae above may be located in the para-position relative to the oxyalkylated group, and the resultant formula may be represented by structure: wherein variables R 2 to R 5 , and n are defined previously.
  • the oxyalkylated hydrocarbyl phenol of the disclosed technology may be represented by the formula: wherein R 4 may be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R 2 , R 3 , R 5 ,and n are defined previously.
  • the polyisobutenyl group may have a number average molecular weight of 250 to 2500, or 350 to 2300, or 500 to 2000. In one embodiment the polyisobutenyl group has a number average molecular weight of 800 to 1100 or 850 to 1050.
  • the polypropenyl group may have a number average molecular weight of 740 to 1200, or 800-850. In one embodiment the polypropenyl group has a number average molecular weight of 825.
  • the oxyalkylated hydrocarbyl phenol of the disclosed technology may be represented by the formula: wherein R 4 may be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R 2 , R 3 , R 5 , and n, are defined previously.
  • the polyisobutenyl group may have a number average molecular weight of 250 to 2500, or 350 to 2300, or 500 to 2000. In one embodiment the polyisobutenyl group has a number average molecular weight of 800 to 1100 or 850 to 1050.
  • the oxyalkylated group of the oxyalkylated hydrocarbyl phenol has formula - (R 1 O) n -, wherein R 1 may be an ethylene, propylene, butylene group, or mixtures thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5.
  • the oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either a homopolymer or copolymer or oligomers thereof. If the oxyalkylated group is in the form of a copolymer, or oligomer thereof, the oxyalkylated group may have either random or block architecture.
  • the oxyalkylated group (or R 1 may be a propylene, or butylene group i.e., the oxyalkylated group does not require an ethylene group. If an ethylene group is present the oxyalkylate group may be a copolymer, or oligomer thereof with either propylene or butylene oxide i.e., blocks of (i) -CH 2 CHzO- with (ii) -CH 2 CH 2 CH 2 CH 2 O- or -CH 2 CH(CH 2 CH 3 )O- or -CH 2 CH(CH 3 )O-.
  • the oxyalkylated group may be based upon propylene oxide.
  • the oxyalkylated hydrocarbyl phenol may be prepared by reacting a hydrocarbyl substituted phenol with an alkylene oxide (typically ethylene oxide, propylene oxide or butylene oxide), optionally in the presence of a base catalyst. Typically the reaction occurs in the presence of a base catalyst.
  • alkylene oxide typically ethylene oxide, propylene oxide or butylene oxide
  • the base catalyst may include sodium chloroacetate, sodium hydride or potassium hydroxide.
  • the aliphatic hydrocarbyl group (also represented by R 4 ) may be linear or branched, typically with at least one branching point.
  • the aliphatic hydrocarbyl group typically has one, although it may in some embodiments be desirable to have to R 4 groups, with the second group being methyl. If a second R 4 group is present and is methyl, then the oxyalkylated hydrocarbyl phenol is a cresol.
  • the oxyalkylated hydrocarbyl phenol of the disclosed technology may be present in an amount ranging from 0.4 wt% to 5 wt%, or 0.5 to 3 wt%, or 0.8 to 2.0 wt% of the lubricating composition.
  • the oxyalkylated hydrocarbyl phenol may be present in an amount from 0.5 to 2.0 wt% of the lubricating composition.
  • the ashless, sulfur free hydrocarbyl phenolic compound may further comprise, in addition to the oxyalkylated hydrocarbyl phenolic compound discussed above, an ashless, hydrocarbyl phenolic antioxidant.
  • Useful hydrocarbyl phenolic antioxidant may include a simple alkyl phenol, a hindered phenol, or coupled phenolic compounds.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • Suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl- 2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert- butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, or butyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate.
  • 2,6-dialkyl phenols may include those wherein each alkyl group is independently selected from alkyl groups having 2 to 16 or 2 to 12 or 2 to 8 or 3 to 5 carbon groups.
  • the hindered phenol antioxidant may be an ester and may include, e.g., Irganox TM L-135 from Ciba.
  • Coupled phenols often contain two alkylphenols coupled with alkylene groups to form bisphenol compounds.
  • suitable coupled phenol compounds include 4,4'-methylene bis-(2,6-di-tert-butyl phenol), 4-methyl-2,6-di-tert-butylphenol, 2,2'-bis-(6-t-butyl-4-heptylphenol); 4,4'-bis(2,6-di-t-butyl phenol), 2,2'-methylenebis(4- methyl-6-t-butylphenol), and 2,2'-methylene bis(4-ethyl-6-t-butylphenol).
  • Phenols of the invention also include polyhydric aromatic compounds and their derivatives.
  • suitable polyhydric aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7 -dihydroxy naphthoic acid, and mixtures thereof.
  • the ashless, hydrocarbyl phenolic antioxidant comprises a hindered phenol.
  • the hindered phenol is derived from 2,6-dialkyl phenol
  • the ashless, hydrocarbyl phenolic antioxidant is 2,6 ditertbutyl phenol
  • the lubricating composition of the invention comprises an ashless, alkylated phenolic antioxidant in a range of 0.1 wt% to 3.0 wt%, or 0.1 wt% to 1.5 wt%, or 0.2 wt% to 1.2 wt%, or 0.5 wt% to 1.2 wt% of the lubricating composition.
  • the ashless, sulfur free hydrocarbyl phenolic compound may further comprise, in addition to the oxyalkylated hydrocarbyl phenolic compound discussed above, an ashless, hydrocarbyl phenolic detergent.
  • Ashless phenolic detergents are extensively taught in PCT Publication WO10/101801 and U.S. Patent 5,827,805 .
  • Suitable ashless phenolic detergents are those that contain a quaternary pnictogen cation, in the absence of ash contributing metal cation.
  • the anion portion of the detergent will be an organic anion having at least one aliphatic hydrocarbyl group of sufficient length to impart oil solubility to the detergent.
  • aliphatic is intended to encompass “alicyclic.” That is, the aliphatic hydrocarbyl groups may be linear, branched, or cyclic or may contain carboxylic moieties, but are to be distinguished from “aromatic” groups, which are not to be considered “aliphatic.”).
  • Suitable aliphatic hydrocarbyl groups if they are in the form of a substituent on an aromatic ring (as in alkylphenates or alkylbenzenesulfonates) may contain 4 to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms.
  • the sulfur-free anionic portion of the detergent may thus be any of the anions derived from the acidic, phenolic organic materials that are used to prepare conventional detergents. As mentioned above, these include phenols, providing phenate detergents with phenate anions, hydrocarbyl-substituted salicylic acids, providing salicylate detergents with salicylate anions, as well as salixarate, and saligenin detergents, and mixtures thereof.
  • the lubricating composition may comprise an ashless, sulfur free phenolic detergent in a range of 0.1 wt% to 0.9 wt%, or 0.1 wt% to 0.7 wt%, or 0.2 wt% to 0.6 wt%, or 0.2 wt% to 0.5 wt% of the lubricating composition.
  • the lubricating composition further comprises an ashless dispersant, which may comprise mixture of ashless dispersants.
  • the dispersant may comprise one or more of (i) the reaction products of a conventional polyolefin acylating agent and an aromatic amine, aliphatic amine, or mixtures thereof, and (ii) the reaction product of a high-vinylidene polyisobutylene acylating agent and an amine, preferably a polyamine.
  • the dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof.
  • the dispersant may be present as a single dispersant.
  • the dispersant may be present as a mixture of two or more (typically two or three) different dispersants, wherein at least one may be a succinimide dispersant.
  • Acylating agents are compounds that can provide an acyl group in an acylation reaction.
  • Typical examples of acylating agents are, for example, succinic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, reactive equivalents and derivatives thereof.
  • the acylating agent may be a polyolefin acylating agent prepared from a conventional polyolefin.
  • Conventional polyolefins are derived from polymerized C 2 -C 6 mono olefins.
  • the polymers may be homopolymers, copolymer or interpolymers.
  • the preferred polyolefin is polyisobutylene (PIB) formed by polymerizing the C 4 -raffinate of a cat cracker or ethylene plant butane/butene stream using aluminum chloride or other acid catalyst systems.
  • PIB polyisobutylene
  • the polyolefin made in this manner is termed a conventional polyisobutylene (PIB) and is characterized by having unsaturated end groups shown in Table 1 with estimates of their mole percents based on moles of polyisobutylenes.
  • the structures are as shown in EPO 355 895 .
  • Conventional PIBs are available commercially under numerous trade names including Parapol ® from Exxon and Lubrizol ® 3104 from Lubrizol.
  • the number average molecular weight (Mn) range of the polyolefins is from about 300-10,000 or even up to 50,000. However, for instance, the preferred range for polyisobutylenes is Mn of about 300-5,000 and the most preferred upper limit Mn is in the range of about Mn 300-2,500.
  • the polyolefin may be prepared from polymerisable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Often, the polymerisable monomers comprise one or more of propylene, isobutene, 1-butene, isoprene, 1, 3-butadiene, or mixtures thereof.
  • reaction products of a conventional polyolefin acylating agent and an aromatic amine, aliphatic amine, or mixtures thereof can encompass both mixtures of aromatic containing and aliphatic containing conventional polyolefin acylating agents and a mixture of conventional polyolefin acylating agents wherein single agents contain either one or a mixture of aromatic and aliphatic amines.
  • aliphatic amine refers to a molecule containing nitrogen in which none of the nitrogens are aromatic.
  • the aliphatic amine may be an aliphatic polyamine such as ethylene polyamine (i.e., a poly(ethyleneamine)), a propylene polyamine, a butylene polyamine, or a mixture of two or more thereof.
  • the aliphatic polyamine may be ethylene polyamine.
  • the aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, or a mixture of two or more thereof.
  • reaction products of (i) with aliphatic amines may be succinimide dispersants, succinamide dispersants, succinic acids, amides, or ester-amides, or mixtures thereof.
  • the reaction products of (i) with aliphatic amines may also be polyolefin succinic acid esters, amides, or ester-amides.
  • a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof.
  • a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as a polyamine, typically diethylenetriamine, polyamine still bottoms, tetraethylenepentamine (TEPA), and the like).
  • reaction products of (i) with aliphatic amines may be N-substituted long chain alkenyl succinimides.
  • An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide, that is, a polyisobutene substituted succinimide dispersant.
  • Succinimide dispersants and their preparation are disclosed, for instance in US Patents 3,172,892 , 3,219,666 , 3,316,177 , 3,340,281 , 3,351,552 , 3,381,022 , 3,433,744 , 3,444,170 , 3,467,668 , 3,501,405 , 3,542,680 , 3,576,743 , 3,632,511 , 4,234,435 , RE26,433 , 6,165,235 , 7,238,650 and EP Patent Publication 0 355 895 A .
  • the reaction products of (i) may contain aromatic amines.
  • aromatic amine refers to a molecule containing at least one aromatic nitrogen.
  • an aromatic nitrogen is a nitrogen either within an aromatic ring or directly bonded to an aromatic ring.
  • aromatic nitrogen refers only to nitrogen directly bonded to an aromatic ring.
  • Aromatic amines may have one or more aromatic moieties linked by a hydrocarbylene group and/or a heteroatom such as N-phenyl-1,4-phenylenediamine (4-amino diphenylamine).
  • the aromatic amine may be a nitro-substituted aromatic amine.
  • Examples of nitro-substituted aromatic amines may include 2-nitroaniline, 3-nitroaniline, and 4-nitroaniline. 3-nitroaniline may be particularly useful.
  • Other aromatic amines may be present along with the nitroaniline. Condensation products with nitroaniline and optionally also with Disperse Orange 3 (that is, 4-(4-nitrophenylazo)aniline) are disclosed in U.S. Publication 2006/0025316 .
  • the amine may be an amine having at least 2, or at least 3, or at least 4 aromatic groups, for instance, from about 4 to about 10, or from about 4 to about 8, or from about 4 to about 6 aromatic groups, and at least one primary or secondary amino group or, alternatively, at least one secondary amino group.
  • the amine may comprise both a primary and at least one secondary amino group.
  • the amine may comprise at least about 4 aromatic groups and at least 2 of any combination of secondary or tertiary amino groups.
  • An example of an amine having 2 aromatic groups is N-phenyl-p-phenylenediamine.
  • An example of an amine having at least 3 or 4 aromatic groups may be represented by Formula (1): wherein, independently, each variable is as follows: R 1 may be hydrogen or a C 1-5 alkyl group (typically hydrogen); R 2 may be hydrogen or a C 1-5 alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic group (when U is aliphatic, the aliphatic group may be a linear or branched alkylene group containing 1 to about 5, or 1 to about 2 carbon atoms); and w may be from 1 to about 10, or 1 to about 4, or 1 to 2 (typically 1). When U is an aliphatic group, U may be an alkylene group containing 1 to about 5 carbon atoms.
  • the amine may also be represented by Formula (1a)
  • each variable U, R 1 , and R 2 are the same as described above and w is 0 to about 9, or 0 to about 3, or 0 to about 1 (typically 0).
  • aromatic amines suitable to be employed in the reaction products of (i) can be found in U.S. Patent 7,253,231 to Devlin at al., issued August 7, 2007 , the content of which are incorporated herein by reference.
  • At least 10 mol% of the reaction products of (i) can contain an aromatic amine. In another embodiment, at least 10 mol% but not more than 60 mol% of the reaction products of (i) can contain an aromatic amine. Preferably, at least 15 mol% but no more than 50 mol% can contain an aromatic amine, and most preferably at least 20 mol% and no more than 40 mol% contain an aromatic amine. In another embodiment, greater than 30 mol% of the reaction products of (i) can contain an aromatic amine, or from 30 mol% to about 80 mol%, or 40 mol% to about 95 mol%.
  • the dispersant mixture may comprise a mixture of (1) the reaction product of a succinated polyisobutylene with one or more polyethylenepolyamines, wherein the polyisobutylene has an average of between 1.2 and 1.6 succinic acid moieties per polymer, and (2) the reaction product of succinated polyisobutylene with one or more aromatic polyamines, such as, for example, 4-amino diphenylamine, wherein the polyisobutylene has an average of between 1.2 and 1.6 succinic acid moieties per polymer.
  • At least 3% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen.
  • at least 10%, or at least 15%, or at least 20 mol% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen.
  • at least 3% but not more than 60 mol% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen.
  • at least 4% but not more than 55% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen, and most preferably at least 5% and no more than 50 mol% can be aromatic nitrogen.
  • the dispersants of (i) may be present in the lubricant composition at a concentration in the range from about 0.01 wt% to about 20 wt%, or from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, or from about 1 wt% to about 6 wt%, or from about 1 to about 3 wt% of the lubricating composition.
  • the dispersant of (i) is present at about 2.0, or 2.5, or 3.0 wt.%.
  • the high vinylidene polyisobutylene acylating agent of (ii) can be derived from a high vinylidene polyisobutylene having a number average molecular weight (Mn) of no more than about 2500 daltons, or no more than 2000 daltons or 1800 daltons, and in one embodiment no more than 1500 daltons or 1250 daltons.
  • Mn number average molecular weight
  • the high vinylidene polyisobutylene acylating agent is reacted with an amine, preferably a polyamine, and preferably an aliphatic polyamine.
  • the aliphatic amine may be an aliphatic polyamine such as ethylene polyamine (i.e., a poly(ethyleneamine)), a propylene polyamine, a butylene polyamine, or a mixture of two or more thereof.
  • the aliphatic polyamine may be ethylene polyamine.
  • the aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, or a mixture of two or more thereof.
  • High vinylidene PIBs generally can contain greater than about 50 mole%, 60 mole%, or 70 mole% or greater and usually about 80 mole% or greater or 90 mole% or greater of alpha-vinylidene and/or beta- double bond isomer and about 1 to 10 mole% of tetrasubstituted double bond isomer.
  • the high vinylidene PIB has an alpha- and/or beta-vinylidene double bond isomer content of 55 mole% or greater, and in other embodiments has an alpha-vinylidene and/or beta- double bond isomer content of 65, of 75, or of 85 mole% or greater.
  • High vinylidene PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition with a milder acidic polymerization catalyst such as BF 3 .
  • High vinylidene PIBs are available commercially from several producers including BASF and Texas Petroleum Chemicals.
  • the polyolefin is a high vinylidene polyolefin
  • the polyolefin can have an average of between about 0.5 and 1.0 acylating agent moieties per polymer.
  • the dispersant mixture may comprise a PIB-succinimide wherein the PIB from which the PIB-succinimide is derived contains at least 50mol% methylvinylidene terminated molecules.
  • the dispersants of (ii) may be present in the lubricant composition at a concentration in the range from about 0.01 wt% to about 20 wt%, or from about 0.1 wt% to about 15 wt%, or from about 2.0 wt% to about 10 wt%, or from about 1 wt% to about 8 wt%, or from about 2 to about 8 wt% of the lubricating composition.
  • the dispersant of (i) is present at about 6.5 or 7.0 or 8.0 wt.%.
  • Dispersants derived from the reaction product of a high vinylidene polyisobutylene acylating agent and an amine and their preparation are disclosed in WO Publication 2013/122898 .
  • 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
  • boron compounds such as boric acid
  • urea such as urea
  • thiourea dimercaptothiadiazoles
  • carbon disulphide aldehydes
  • ketones carboxylic acids such as terephthalic acid
  • hydrocarbon-substituted succinic anhydrides such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the post-treated dispersant is borated.
  • the post-treated dispersant is reacted with dimercaptothiadiazoles.
  • the post-treated dispersant is reacted with phosphoric or phosphorous acid.
  • the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Public
  • the dispersant may be borated or non-borated.
  • the dispersant may comprise a blend of borated and non-borated dispersants.
  • a borated dispersant may be a succinimide dispersant.
  • the ashless dispersant is boron-containing, i.e., has incorporated boron and delivers said boron to the lubricant composition.
  • the borated dispersant contains from 0.1% to 5%, or from 0.5% to 4%, or from 0.7% to 3% by weight boron.
  • the borated dispersant may be a borated acylated amine, such as a borated succinimide dispersant. Borated dispersants are described in U.S.
  • Borated dispersant are prepared by reaction of one or more dispersants with one or more boron compounds. Any of the dispersants described herein may be borated, either during the reaction of the hydrocarbyl substituted acylating agent and the amine or after.
  • the boron compound may be an alkali or mixed alkali metal and alkaline earth metal borate.
  • These metal borates are generally hydrated particulate metal borates which are known in the art.
  • Alkali metal borates include mixed alkali and alkaline metal borates.
  • U.S. Patents 3,997,454 , 3,819,521 , 3,853,772 , 3,907,601 , 3,997,454 and 4,089,790 disclose suitable alkali and alkali metal and alkaline earth metal borates and their methods of manufacture.
  • the boron compound is boric acid.
  • the boron-containing dispersant may be present in an amount to deliver at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm boron to the lubricant composition.
  • the lubricant composition is free of a boron-containing dispersant, i.e., delivers no more than 10 ppm boron to the final formulation.
  • the lubricating composition of the disclosed technology may further include other additives.
  • the disclosed technology provides a lubricating composition further comprising at least one of dispersant other than an ashless dispersant discussed above, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a foam inhibitor, a demulsifier, a pour point depressant or mixtures thereof.
  • Antioxidants include sulfurized olefins, diarylamines, alkylated diarylamines, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxyl thioethers, or mixtures thereof.
  • the lubricating composition includes an antioxidant, or mixtures thereof.
  • the antioxidant may be present at 0 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 5 wt%, or 0.5 wt% to 3 wt%, or 0.3 wt% to 1.5 wt% of the lubricating composition.
  • the diarylamine or alkylated diarylamine may be a phenyl- ⁇ -naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, dioctyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • the lubricating composition may be a lubricating composition further comprising a molybdenum compound.
  • the molybdenum compound may be an antiwear agent or an antioxidant.
  • the molybdenum compound may be be chosen from molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
  • the molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • molybdenum dithiocarbamates which may be used as an antioxidant, include commercial materials sold under the trade names such as Vanlube 822 TM and Molyvan TM A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube TM S-100, S-165, S-600 and 525, or mixtures thereof.
  • the lubricating composition further includes a viscosity modifier.
  • the viscosity modifier is known in the art and may include hydrogenated styrenebutadiene rubbers, ethylene-propylene copolymers, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkyl styrenes, polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in PCT Publication WO2010/014655 ), esters of maleic anhydride-styrene copolymers, or mixtures thereof.
  • the dispersant viscosity modifier may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized with an amine, or styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in PCT Publication WO2006/015130 or U.S. Patents 4,863,623 , 6,107,257 , 6,107,258 , 6,117,825 and 7,790,661 . In one embodiment, the dispersant viscosity modifier may include those described in U.S.
  • dispersant viscosity modifier may include those described in U.S. Patent 7,790,661 column 2, line 48 to column 10, line 38.
  • the lubricating composition of the disclosed technology further comprises a dispersant viscosity modifier.
  • the dispersant viscosity modifier may be present at 0 wt% to 5 wt%, or 0 wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.2 wt% to 1.2 wt% of the lubricating composition.
  • the friction modifier may be be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides.
  • the friction modifier may be present at 0 wt% to 6 wt%, or 0.01 wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.1 wt% to 2 wt% of the lubricating composition.
  • fatty alkyl or "fatty” in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
  • Suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • the lubricating composition optionally further includes at least one antiwear agent.
  • suitable antiwear agents include titanium compounds, tartaric acid derivatives such as tartrate esters, amides or tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
  • the antiwear agent may in one embodiment include a tartrate or tartrimide as disclosed in PCT Publication WO2006/044411 or Canadian Patent 1,183,125 .
  • the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8.
  • the antiwear agent may in one embodiment include a citrate as is disclosed in US Publication 2005-0198894 .
  • the lubricating composition may further include a phosphorus-containing antiwear agent.
  • the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the antiwear agent may be present at 0 wt% to 3 wt%, or 0.1 wt% to 1.5 wt%, or 0.5 wt% to 0.9 wt% of the lubricating composition.
  • the oil soluble titanium compound may be a titanium (IV) alkoxide.
  • the titanium alkoxide may be formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium alkoxide may be titanium (IV) isopropoxide.
  • the titanium alkoxide may be titanium (IV) 2-ethylhexoxide.
  • the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol.
  • the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid may be oleic acid.
  • the oil soluble titanium compound may be a titanium carboxylate.
  • the titanium (IV) carboxylate may be titanium neodecanoate.
  • Foam inhibitors that may be useful in the compositions of the disclosed technology include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • Pour point depressants that may be useful in the compositions of the disclosed technology include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof different from the non-hydroxy terminated acylated polyalkylene oxide of the disclosed technology.
  • Metal deactivators include derivatives of benzotriazoles (typically tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles.
  • the metal deactivators may also be described as corrosion inhibitors.
  • Seal swell agents include sulpholene derivatives Exxon Necton-37 TM (FN 1380) and Exxon Mineral Seal Oil TM (FN 3200).
  • the lubricating composition of the disclosed technology may also include a boron containing compound.
  • the boron containing compound may be selected from borated dispersants discussed above, borated friction modifiers, and mixtures thereof.
  • the boron-containing compound may include a borate ester or a borated alcohol.
  • the boron containing compound may be present in an amount to deliver at least 25 ppm to 2000 ppm, and in one embodiment 25 ppm to 600 ppm, and in one embodiment 25 ppm to 300 ppm, and in one embodiment 100 ppm to 200 ppm and in one embodiment, at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm boron to the lubricant composition.
  • the lubricant composition may be free of a boron-containing compound, i.e. all components deliver no more than 10 ppm boron to the final formulation.
  • An engine lubricating composition in different embodiments may have a composition as disclosed in the following table 2: Table 2 Additive Embodiments (wt%) A B C Alkaline earth metal sulfonate detergent 0.2 to 2.8 0.2 to 2.5 0.6 to 1.8 Ashless, sulfur free, hydrocarbyl phenolic compound 0.4 to 8 0.4 to 6 0.4 to 6 Ashless Dispersant 0 to 12 0 to 8 0.5 to 6 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2 Antioxidant 0.1 to 13 0.1 to 10 0.5 to 5 Antiwear Agent 0.1 to 15 0.1 to 10 0.3 to 5 Friction Modifier 0.01 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to 8 0 to 6 Oil of Lubricating Viscosity Balance to 100% Balance to 100% Balance to 100% Table 1 - exemplary engine lubricating composition.
  • Table 2 Additive Embodiments (
  • An ashless sulphur free hydrocarbyl phenolic compound may comprise the following components disclosed in the following table 3 (wt% with respect to the total amount of ashless, sulfur free, hydrocarbyl phenolic compound on an oil free basis).
  • Table 3 Exemplary ashless, sulfur free, hydrocarbyl phenolic compounds Additive Embodiments (wt%)
  • Table 2 - exemplary ashless sulfur free hydrocarbyl phenolic compositions
  • the disclosed technology provides a method of lubricating an internal combustion engine.
  • the engine components may have a surface of steel or aluminum.
  • An aluminum surface may be derived from an aluminum alloy that may be a eutectic or a hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials).
  • the aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
  • the internal combustion engine is the engine in a heavy duty vehicle.
  • a heavy duty vehicle (HDV) containing the internal combustion engine of the present invention may have a laden mass (sometimes referred to as gross vehicle weight rating (GVWR)) of over 2700 kg (or 6000 USA pounds), or over 2900 kg, or over 3000 kg, or over 3300 kg, or over 3500 kg, or over 3700 kg, or over 3900 kg (or 8500 USA pounds).
  • GVWR gross vehicle weight rating
  • the upper limit on the laden mass or GVWR is set by national government and may be 10000 kg, or 9000 kg, or 8000 kg, or 7500 kg.
  • the upper ranges of laden mass may be up to 400,000 kg, or up to 200,000 kg, or up to 60,000 kg, or up to 44,000 kg, or up to 40,000 kg.
  • a laden mass above 120,000 is for an off-highway vehicle.
  • the vehicle containing the internal combustion engine having a laden mass of over 2700 kg (or 3,500 kg) may be a heavy duty diesel engines equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines.
  • NG positive ignition natural gas
  • LPG low-duty diesel engines
  • the European Union indicates that for new light duty vehicles (passenger cars and light commercial vehicles) included within the scope of ACEA testing section "C" have a "technically permissible maximum laden mass" not exceeding 2610 kg.
  • the internal combustion engine may be a diesel engine suitable for powering a vehicle having a laden mass over 3,500 kg.
  • the internal combustion engine is a heavy duty diesel compression ignition (or spark assisted compression ignition) internal combustion engine.
  • the internal combustion engine may be a diesel fueled engine.
  • Diesel fueled engines may be fueled with a mixture of conventional diesel fuel and bio-derived diesel fuel (i.e., bio-diesel).
  • the diesel engine fuel may comprise 5 volume percent to 100 volume percent bio-diesel (i.e., B5 to b100); in one embodiment the diesel fuel comprises 5 volume percent to 50 volume percent bio-diesel or 8 volume percent to 30 volume percent bio-diesel.
  • the diesel fuel is substantially free of (i.e., contains less than 1 volume percent) bio-diesel.
  • the internal combustion engine may be a heavy duty diesel engine.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content.
  • the sulfur content of the engine oil lubricant may be 1 wt% or less, or 0.8 wt% or less, or 0.5 wt% or less, or 0.3 wt% or less. In one embodiment, the sulfur content may be in the range of 0.001 wt% to 0.5 wt%, or 0.01 wt% to 0.3 wt%.
  • the phosphorus content may be 0.2 wt% or less, or 0.12 wt% or less, or 0.1 wt% or less, or 0.085 wt% or less, or 0.08 wt% or less, or even 0.06 wt% or less, 0.055 wt% or less, or 0.05 wt% or less. In one embodiment, the phosphorus content may be 0.04 wt% to 0.12 wt%. In one embodiment, the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulfated ash content may be 0.3 wt% to 1.2 wt%, or 0.5 wt% to 1.2 wt% or 1.1 wt% of the lubricating composition. In one embodiment, the sulfated ash content may be 0.5 wt% to 1.2 wt% of the lubricating composition.
  • the TBN (as measured by ASTM D2896) of the engine oil lubricant may be 3 mg KOH/g to 15 mg KOH/g, or 4 mg KOH/g to 12 mg KOH/g, or 5 mg KOH/g to 10 mg KOH/g, or 7 mg KOH/g to 10 mg KOH/g.
  • the lubricating composition may be an engine oil, wherein the lubricating composition may be characterized as having at least one of (i) a sulfur content of 0.5 wt% or less, (ii) a phosphorus content of 0.12 wt% or less, and (iii) a sulfated ash content of 0.5 wt% to 1.1 wt% of the lubricating composition.
  • a lubricating composition taught herein for lubricating a compression ignition, internal combustion engine is disclosed.
  • Use of the lubricating composition may be to provide one of (i) fuel economy, (ii) corrosion, (iii) cleanliness, (iv) bore wear and (v) seal protection.
  • Polyisobutylene (950 Mn) phenol (1 wt. eq.) was charged into a reactor, and heated to 175 F.
  • KOH pellets 0.0075 wt. eq.
  • Full vacuum was applied to remove the water generated. The content was them cooled to 245 F.
  • Propylene oxide (0.235 wt. eq.) was charged to the reaction vessel slowly while maintaining the temperature between 245 F and 255 F. Once the reaction finished.
  • Magnesol and Celite was added to the reaction mixture, which was stirred for addition 4 hr at 250 F. The mixture was filtered through Celite to afford the product.
  • a series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 5.
  • BL-1 employs both low soap sulfonate detergents and high soap sulfonate detergents.
  • high soap sulfonate detergent was replaced with low soap detergents, (BL-2) at equal ash
  • the % soap went down and the TBN (D2896 & D4739) went up as a result.
  • inventive examples EX-1 & EX-2 were top treated with oxyalkylated hydrocarbyl phenol (Example F).
  • EX-3 & EX-4 the phenated detergents were replaced with Ca salicylate as equal ash.
  • a series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 8.
  • Table 8 Lubricating Oil Compositions 1 BL-3 EX-5 Group II Base Oil Balance to 100% Balance to 100% Low soap sulfonate detergents 2 1.45 1.71 High soap sulfonate detergents 2 0.75 0.25 Zinc dialkyldithio phosphate 0.8 0.8 Active Dispersants 3 1.95 1.95 Viscosity Modifier 4 0.98 0.98 Antioxidants 5 0.60 0.60 Additional additives 6 0.23 0.23 Phenolic AO 7 0.2 0.2 Oxyalkylated hydrocarbyl phenolic compound 8 1 1. All concentrations are on an oil free (i.e. active basis) 2. Ca or Mg alkylsulfonates. 3. 2000 Mn PIBsuccinimide dispersants 4.
  • BL-3 employs high level of high soap sulfonate detergents.
  • high soap sulfonate detergent was partially replaced with low soap detergents (EX-5) at equal ash, the % soap went down and the TBN (D2896 & D4739) went up as a result.
  • the inventive examples EX-5 was also treated with oxyalkylated hydrocarbyl phenol (Example F).
  • the lubricants described above are evaluated in cleanliness bench tests MHT TEOST & Sludge bench test.
  • MHT TEOST evaluates the oxidation and deposit forming tendency of the engine oils.
  • Sludge bench test evaluates the sludge dispersing capability of an engine oil. The overall the results obtained for each lubricant are as follows: Table 10 - Bench Test Performance BL-3 EX-5 MHT TEOST mg 49 37 Sludge Rating 68 79
  • a series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 11.
  • Table 11 Lubricating Oil Compositions 1 EX-6 Group II Base Oil Balance to 100% Low soap high TBN sulfonate detergents 2 1.1 Zinc dialkyldithiophosphate 1.1 Active Dispersants 3 4.6 Viscosity Modifier 4 0.96 Antioxidants 5 2.0 Additional additives 6 0.66 Phenolic AO 7 0.8 Oxyalkylated hydrocarbyl phenolic compound 8 1.2 1. All concentrations are on an oil free (i.e. active basis) 2. Ca or Mg alkylsulfonates. 3. 2000 Mn PIB succinimide dispersants 4. Including viscosity modifiers and dispersant viscosity modifiers. 5. Aminic antioxidants & sulfurized olefins 6.
  • Additional additives include friction modifiers, foam inhibitors, corrosion inhibitors etc. 7. Hinder phenol antioxidants 8.
  • Example F Table 12 - Lubricating Oil Characterization EX-6 % Phosphorus 1.1 % Sulfated Ash 0.98 % Soap 0.52 %
  • Example F 1.2 D2896 10 D4739 6.6
  • the disclosed technology is capable of at least one of (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness (typically control of deposits, typically control/reduction of soot), (iv) control of bore wear and (v) protection of seals, typically in a heavy duty diesel internal compression combustion engine.

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Claims (27)

  1. Composition lubrifiante comprenant :
    a) une huile de viscosité lubrifiante ;
    b) un détergent sulfonate de métal alcalino-terreux ayant un rapport métallique d'au moins 10, en une quantité pour contribuer de 3 à 14 g KOH/kg de TBN tel que mesuré selon la norme ASTM D2986-11 à la composition lubrifiante ;
    c) un composé phénolique hydrocarbyle sans cendres, sans soufre, en une quantité allant de 0,4 % en poids à 6,0 % en poids de la composition ; et
    d) un agent dispersant sans cendres ;
    dans laquelle la composition lubrifiante contient des cendres totales de 0,3 à 1,8 % en poids ;
    dans laquelle la composition lubrifiante contient un savon détergent total en une quantité allant de 0,1 à 0,9 % en poids ; dans laquelle la composition lubrifiante contenant moins de 0,1 % en poids d'un détergent phénate contenant du soufre ;
    dans laquelle la composition lubrifiante comprend moins de 0,1 % en poids d'un détergent sulfonate de métal alcalino-terreux ayant un rapport métallique inférieur à 10 ; et
    dans laquelle le composé phénolique hydrocarbyle sans cendres, sans soufre, comprend un composé hydrocarbylphénol oxyalkylé.
  2. Composition lubrifiante selon la revendication 1, dans laquelle le composé hydrocarbylphénol oxyalkylé comprend un groupe hydrocarbyle contenant de 25 à 200 ou de 25 à 175 ou de 25 à 140, ou de 30 à 100 atomes de carbone.
  3. Composition lubrifiante selon la revendication 1 ou la revendication 2, dans laquelle l'hydrocarbylphénol oxyalkylé est un composé phénolique polyisobutylène oxyalkylé.
  4. Composition lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle le groupe oxyalkylé du composé hydrocarbylphénol oxyalkylé a la formule -(R1O)n-, dans laquelle chaque R1 est choisi indépendamment dans le groupe constitué d'un groupe éthylène, un groupe propylène et un groupe butylène ; et n peut valoir indépendamment de 1 à 50, ou de 1 à 20, ou de 1 à 10, ou de 2 à 5.
  5. Composition lubrifiante selon la revendication 1 ou la revendication 2, dans laquelle le composé hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0028
     dans laquelle
    chaque R2 peut être indépendamment un hydrogène ou un groupe hydrocarbyle ayant de 1 à 6 atomes de carbone ; R3 peut être de l'hydrogène, un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ou un groupe acyle représenté par -C(=O)R5 ;
    R5 peut être un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ;
    chaque R4 peut être indépendamment un groupe hydrocarbyle ayant de 25 à 200, de 25 à 175, de 25 à 140, ou de 30 à 100, ou de 40 à 96 atomes de carbone ;
    n = 1 à 20, ou 1 à 10 ; et
    m = 1 à 3.
  6. Composition lubrifiante selon la revendication 5, dans laquelle l'hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0029
     dans laquelle
    chaque R2 peut indépendamment être de l'hydrogène ou du méthyle ;
    R3 peut être de l'hydrogène, un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ou un groupe acyle représenté par -C(=O)R5 ;
    R5 peut être un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ;
    R4 peut être un groupe hydrocarbyle ayant de 25 à 200 atomes de carbone ;
    n = 1 à 20, ou 1 à 10 ; et
    m = I.
  7. Composition lubrifiante selon la revendication 6, dans laquelle l'hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0030
     dans laquelle
    chaque R2 peut indépendamment être de l'hydrogène ou du méthyle ;
    R3peut être de l'hydrogène, un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ou un groupe acyle représenté par -C(=O)R5 ;
    R5 peut être un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ;
    R4 peut être un groupe polyalk(èn)yle contenant de 25 à 200, ou de 25 à 175, ou de 25 à 140, ou de 30 à 100,
    ou de 40 à 96 atomes de carbone ;
    n = 1 à 8, ou 2 à 8 ; et
    m = I.
  8. Composition lubrifiante selon la revendication 7, dans laquelle l'hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0031
     dans laquelle
    chaque R2 peut indépendamment être de l'hydrogène ou du méthyle ;
    R3 peut être de l'hydrogène, un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ou un groupe acyle représenté par -C(=O)R5 ;
    R5 peut être un groupe hydrocarbyle ayant de 1 à 24 atomes de carbone ;
    R4 peut être un groupe polyisobutényle contenant de 25 à 200, ou de 25 à 175, ou de 25 à 140, ou de 30 à 100,
    ou de 40 à 96 atomes de carbone ;
    n = 1 à 8, ou 2 à 8 ou 3 à 5 ; et
    m = I.
  9. Composition lubrifiante selon l'une quelconque des revendications 5 à 8, dans laquelle l'hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0032
     et R2, R3, n et R4 sont tels que définis précédemment.
  10. Composition lubrifiante selon l'une quelconque des revendications 5 à 7, dans laquelle l'hydrocarbylphénol oxyalkylé est représenté par la formule :
    Figure imgb0033
     dans laquelle R4 est un groupe polyoléfinique (typiquement un groupe polypropényle ou polyisobutényle) et R2, n et R3 sont tels que définis précédemment.
  11. Composition lubrifiante selon la revendication 10, dans laquelle le groupe polyoléfinique a un poids moléculaire moyen en nombre allant de 250 à 2500, ou de 350 à 2300, ou de 500 à 2 000.
  12. Composition lubrifiante selon la revendication 11, dans laquelle le groupe polyoléfinique 1s est un groupe polyisobutényle.
  13. Composition lubrifiante selon la revendication 11, dans laquelle le groupe polyoléfinique 1s est un groupe polypropényle.
  14. Composition lubrifiante selon l'une quelconque des revendications 1 à 13, dans laquelle le composé phénolique hydrocarbyle oxyalkylé est présent en une quantité allant de 0,4 % en poids à 5,0 % en poids de la composition lubrifiante.
  15. Composition lubrifiante selon l'une quelconque des revendications 1 à 14, dans laquelle le composé phénolique hydrocarbyle sans cendres, sans soufre, comprend en outre un antioxydant phénolique alkylé.
  16. Composition lubrifiante selon la revendication 15, dans laquelle l'antioxydant phénolique alkylé est dérivé d'un 2,6-dialkylphénol, dans laquelle chaque groupe alkyle est indépendamment choisi parmi des groupes alkyle contenant de 3 à 8 atomes de carbone.
  17. Composition lubrifiante selon les revendications 15 ou 16, dans laquelle l'antioxydant phénolique alkylé est présent en une quantité allant de 0,1 % en poids à 2,0 % en poids, ou de 0,1 % en poids à 1,5 % en poids, ou de 0,2 % en poids à 1,2 % en poids, ou de 0,5 % en poids à 1,2 % en poids de la composition lubrifiante.
  18. Composition lubrifiante selon l'une quelconque des revendications 1 à 17, dans laquelle le composé phénolique hydrocarbyle sans cendres, sans soufre, comprend en outre un détergent hydrocarbylphénolique choisi dans le groupe constitué de détergents à base de salixarate sans cendres et détergents à base de saligénine sans cendres.
  19. Composition lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle l'agent dispersant sans cendres comprend le produit de réaction d'un agent d'acylation de polyisobutylène à haute teneur en vinylidène et d'une amine, dans laquelle le polyisobutylène contient plus de 50 % molaires, de 60 % molaires, ou de 70 % molaires ou plus et habituellement 80 % molaires ou plus ou 90 % molaires ou plus d'un isomère d'alpha-vinylidène et/ou à double liaison bêta.
  20. Composition lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle le détergent sulfonate de métal alcalino-terreux est choisi dans le groupe constitué de détergents de sulfonate de calcium et détergents de sulfonate de magnésium.
  21. Composition lubrifiante selon l'une quelconque des revendications précédentes, comprenant en outre un composé contenant du bore.
  22. Composition lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle le TBN total de la composition lubrifiante est de 3 à 15 g KOH/Kg tel que mesuré selon la norme ASTM D2986-11.
  23. Composition lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle le taux de phosphore est compris entre 0,04 et 0,12 % en poids.
  24. Procédé de lubrification d'un moteur à combustion interne, comprenant la fourniture au moteur d'une composition lubrifiante selon l'une des revendications précédentes.
  25. Procédé selon la revendication 24, dans lequel le moteur 1s est un moteur à combustion interne à allumage par compression.
  26. Procédé de la revendication 25, dans lequel le véhicule propulsé par le moteur à combustion interne à allumage par compression a une masse maximale en charge supérieure à 3 500 kg.
  27. Utilisation d'une composition lubrifiante selon l'une quelconque des revendications précédentes 1 à 23 pour lubrifier un moteur à combustion interne à allumage par compression afin de fournir au moins l'un parmi (i) le contrôle de l'économie de carburant, (ii) le contrôle de la corrosion, et (iii) la propreté.
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