Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
  • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
  • C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/042—Metal salts thereof
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/45—Ash-less or low ash content
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
  • C10N2040/253—Small diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• aspects of the exemplary embodiment relate to a dispersant viscosity modifier, and more specifically to a sulfonated dispersant viscosity modifier and to a lubricating composition, such as an engine oil, which includes the described dispersant viscosity modifier. Aspects of the exemplary embodiment also relate to a method for use of the described dispersant viscosity modifier to improve the film thickness and/or antiwear performance of such a lubricating composition.
• Lubricating oil compositions desirably maintain a relatively stable viscosity over a wide range of temperatures.
• Viscosity modifiers are often used to reduce the extent of the decrease in viscosity as the temperature is raised or to reduce the extent of the increase in viscosity as the temperature is lowered, or both.
• a viscosity modifier ameliorates the change of viscosity of an oil containing it with changes in temperature. The fluidity characteristics of the oil are thereby improved.
• DVMs dispersant viscosity modifiers
• U.S. Pat. No. 3,642,728, issued February 15, 1972, entitled SULFONATE POLYMERS, by Canter discloses sulfonated polymers, such as polymers with low unsaturation formed by the polymerization of ethylene or propylene, particularly polymers with 0.2-10 mole % remaining unsaturation. Sulfonation can be carried out at an aromatic ring within the backbone or pendent therefrom.
• U.S. Pub. No. 20130303418 published November 14, 2013, entitled HIGH MOLECULAR WEIGHT POLYMERS AS VISCOSITY MODIFIERS, by FALENDER, et al., discloses a lubricating composition which comprises a base oil and between 10 ppm and 1000 ppm by mass of a viscosity modifier, the viscosity modifier comprising an olefin copolymer.
• a viscosity modifier comprising an olefin copolymer.
• additional monomers is anticipated to allow the inventive polymer to have the properties of dispersants, antioxidants, pour point depressants and other additive chemistry.
• U.S. Pub. Nos. 20120178656 and 20120178659, entitled DISPERSANT VISCOSITY MODIFIERS, by Sutton, et al., and Price, et al. disclose a grafted polymer useful as a dispersant viscosity modifier in lubricating compositions.
• the polymer backbone includes an olefin block and a vinyl aromatic block.
• the polymer is grafted with a pendant carbonyl containing group, which may be substituted to provide ester, imide and/or amide functionality.
• a lubricating composition includes an oil of lubricating viscosity and an oil-soluble dispersant viscosity modifier which includes an olefin-based polymer backbone and at least one pendent functional group.
• Each of the at least one pendent functional group is independently attached to the olefin-based polymer backbone by a linking group.
• the at least one pendent functional group includes a sulfonate moiety.
• a process for making a lubricating composition includes: (i) providing an olefin- based polymer backbone with one or more acylating linking groups, each independently attached along the polymer backbone; (ii) optionally, reacting each acylating group with a hydroxy alkyl amine, an alkylene polyamine, a polyol, or a combination thereof, resulting in an olefin-based polymer with one or more linker units each independently attached along the polymer backbone; and (iii) reacting each linking group or linker unit with a hydrocarbyl sulfonate compound, resulting in a dispersant viscosity modifier comprising one or more pendent hydrocarbyl sulfonate groups each independently attached to the olefin-based polymer.
• FIGURE 1 is a Stribeck plot of traction coefficient vs log mean speed (mm/s) for lubricating compositions formed with and without a sulfonated dispersion viscosity modifier;
• FIGURE 2 is a plot of Central Film Thickness (nm) vs speed (m/s) for lubricating compositions formed with and without a sulfonated dispersion viscosity modifier.
• the exemplary embodiment relates to a lubricating composition which includes an oil of lubricating viscosity and a sulfonated dispersant viscosity modifier that includes an olefin-based polymer with pendent groups having sulfonate functionality.
• the exemplary sulfonated dispersant viscosity modifier has improved performance in engine tests, providing a good viscosity index, good soot dispersion and/or toleration properties, while also providing good antiwear protection and/or film thickness performance.
• the exemplary lubricating composition finds particular application as an engine oil for passenger vehicles and heavy duty diesel vehicles.
• the exemplary sulfonated dispersant viscosity modifier is a material that provides viscosity modifier performance in a lubricating composition while also providing dispersant functionality.
• the dispersant viscosity modifier may provide additional and or other benefits to a lubricating composition.
• the exemplary dispersant viscosity modifier is an oil-soluble polymer, which includes a polymer backbone, such as an olefin-based polymer, and one or more pendent hydrocarbyl sulfonate groups each independently attached to the olefin-based polymer.
• the pendent hydrocarbyl sulfonate groups each include a sulfonate moiety, which can be in the form of a sulfonate salt or a sulfonic acid group, and a hydrocarbyl group, such as an alkyl and/or aryl group, which spaces the sulfonate moiety from the polymer backbone and connects it thereto
• oil soluble it is meant that the dispersion viscosity modifier is soluble in oil at least to the amounts described herein for desirable for serving its intended purpose.
• Each of the pendent groups is attached to the polymer chain by a linking group that is grafted onto the olefin-based polymer or forms a part of the polymer backbone.
• the linking group thus links the pendent group to the olefin- based polymer.
• Each linking group may be derived from a dicarboxylic acid, such as maleic anhydride, that can be linked to the pendent group directly or indirectly, via a linker unit.
• the linking group may be grafted to the polymer backbone by first reacting a dicarboxylic acid, such as maleic anhydride, to the polymer backbone using a peroxide catalyst to form the linking group and then attaching the linker unit by esterification, imidation or amidation.
• a dicarboxylic acid such as maleic anhydride
• peroxide catalyst to form the linking group and then attaching the linker unit by esterification, imidation or amidation.
• P represents the olefin-based polymer
• X represents the linking group
• Y represents an optional intermediate linker unit
• Z represents the pendent hydrocarbyl sulfonate group
• x is at least 1 , such as from 1 to 20, or 1 to 10, or 1 to 8, e.g., at least 2.
• the values of x may be considered number average values over all the molecules present.
• a ratio by weight of linking groups X to the polymer backbone P in the dispersant viscosity modifier may be at least 1 :100, or at least 2:100, such as at least 3:100, and in some embodiments, is up to up to 20:100 or up to 10:100.
• P in Formula (I) may contain a range of molecular weights, commonly characterized by a molecular weight distribution, so the values of x may be considered number average values over all the molecules present.
• P is an ethylene-olefin-based copolymer and the viscosity modifier of Formula (I) is represented by Formula (II) or (III):
• each R 1 represents H or an alkyl group containing from 1 to 8 carbon atoms
• n, p and q are independently at least 1 ,
• k is at least 1 , such as at least 2.
• a ratio of m:n may be from 1 to 6.
• the ratio of m:n may be 1.5 to 2.3, or 2.3 to 3.5, or 3.5 to 6.
• a ratio of the number of hydrocarbyl sulfonate groups q : number ethylene olefin units p in the molecules of Formulas (II) and (III) is at least 0.01.
• the ratio of q:p may be at least 0.02, or at least 0.03, or at least 0.1 , or at least 0.2 and may be up to 0.9, or up to 0.5.
• Formula (II) represents a viscosity modifier in which the linking group X is grafted onto the polymer backbone P, which can be of the general form -[(CH 2 )m-(CHR 1 -CH2)n]p- prior to grafting.
• Formula (III) represents a viscosity modifier in which the linking group X is integral with the polymer backbone P.
• linking groups X may be linked to a hydrocarbyl sulfonate group Z, although in one embodiment, a majority (at least 50%), or substantially all (at least 80%, or at least 90%, or at least 95%), or all of the linking groups X are linked to a respective hydrocarbyl sulfonate group Z.
• the hydrocarbyl sulfonate group Z may be derived from a hydrocarbyl sulfonate compound, such as an alkyl or aryl sulfonic acid, source thereof, or salt thereof.
• the hydrocarbyl sulfonate group Z can be represented by the general formula -[R 2 (S0 3 ) ⁇ ] r M r+ , where R 2 represents a hydrocarbyl group, and M r+ represents a cation, where r is at least 1.
• the sulfonate moiety in the hydrocarbyl sulfonate group Z can thus be represented by -[(S0 3 ) ⁇ ] r M r+ .
• M r+ may be selected from H + (the acid form) and other cations, such as metal cations and aliphatic amine cations of the form -(NR 3 R R 5 ), where R 3 , R 4 , and R 5 are independently selected from H and Ci to C 3 o hydrocarbyl groups, such as aliphatic groups, e.g., Ci to C30 alkyl groups.
• R 3 , R 4 , and R 5 are independently selected from H and Ci to C 3 o hydrocarbyl groups, such as aliphatic groups, e.g., Ci to C30 alkyl groups.
• at least one or at least two of R 3 , R 4 , and R 5 is an alkyl group and in another embodiment, each of R 3 , R 4 , and R 5 is an alkyl group.
• the alkyl groups have at least 2, or at least 3, or up to 20, or up to 10 carbon atoms.
• Example metal cations include alkali metals, such as K + , Na + , Mg +2 , Ca 2+ , and mixture thereof.
• the dispersant viscosity modifier is metal free, and the cation is a non-metal cation.
• the cation is suitably a monovalent cation, i.e., r is 1 , although minor amounts of multivalent cations may be present.
• the sulfonate moiety may be selected from oil- soluble salts to avoid formation of oil-insoluble or sparingly soluble salts through reaction with the base.
• hydrocarbyl group is used herein 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. Examples of hydrocarbyl groups include:
• hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
• aliphatic e.g., alkyl or alkenyl
• alicyclic e.g., cycloalkyl, cycloalkenyl
• aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
• 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 (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
• hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
• Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl.
• substituents such as pyridyl, furyl, thienyl, and imidazolyl.
• no more than two, and in some embodiments, no more than one non-hydrocarbon substituent is present for every ten carbon atoms in the hydrocarbyl group. In one embodiment, there are no non-hydrocarbon substituents in the hydrocarbyl group.
• the hydrocarbyl group R 2 of the hydrocarbyl sulfonate group Z is or includes an alkyl group, such as a C 3 to C 24 alkyl group or C3-C20 alkyl group, which spaces the sulfonate moiety from the polymer backbone by at least three carbon atoms, which may be in the form of a chain and/or ring.
• the hydrocarbyl group R 2 is or includes an aryl group, such as a C 6 to C 2 o aryl group which spaces the sulfonate moiety from the polymer backbone by an aromatic ring.
• One or more of the carbons in the hydrocarbyl group R 2 may be substituted with heteroatoms.
• the sulfonated dispersant viscosity modifier includes from 1 to 50 of the described hydrocarbyl sulfonate groups Z, or from 1 to 30, or from 1 to 20, or 1 to 10, or from 1 to 6, or 1 to 4, per molecule of the dispersant viscosity modifier, on average. In some embodiments, the sulfonated dispersant viscosity modifier includes 1 , 2, 3, 4, 5 or 6 hydrocarbyl sulfonate groups Z, on average.
• the exemplary linking groups X are acylating groups, each independently attached along the polymer's backbone.
• the linking group X may be derived from an ethylenically unsaturated carboxylic acid monomer, such as a dicarboxylic acid, or functional equivalent thereof, or a polyol.
• the intermediate linker unit Y may be derived from a hydroxy alkyl amine, an alkylene polyamine, or a combination thereof.
• the linking group X is derived from maleic anhydride and the linker unit Y is derived from a hydroxy alkyl amine.
• the unsaturated carboxylic reactant is grafted on to the olefin-based polymer backbone and the hydroxy alkyl amine and/or alkylene polyamine is reacted with the unsaturated carboxylic reactant group containing olefin-based polymer backbone.
• the unsaturated carboxylic reactant is present in the olefin-based polymer backbone and the hydroxy alkyl amine and/or alkylene polyamine is reacted with the unsaturated carboxylic reactant group containing olefin-based polymer backbone.
• the hydrocarbyl sulfonate compound includes an amine or -OH functional group which can serve as an intermediate linker unit Y.
• the unsaturated carboxylic reactant may be grafted on to the olefin-based polymer backbone and the amine/alcohol functional group of the hydrocarbyl sulfonate compound is reacted with the unsaturated carboxylic reactant group containing olefin-based polymer backbone.
• the amine/alcohol functional group of the hydrocarbyl sulfonate compound is reacted with the unsaturated carboxylic reactant group containing olefin-based polymer backbone.
• the polymer backbone P employed in the sulfonated dispersant viscosity modifier is not particularly limited, provided that it can be modified with a carboxylic acid functionality or a reactive equivalent of the carboxylic acid functionality (e.g., anhydride or ester) that serves as the linking group described above.
• Suitable olefin-based polymer backbones P include ethylene, propylene, and butylene polymers, copolymers thereof, copolymers thereof further containing a non-conjugated diene, and isobutylene/conjugated diene copolymers, each of which can be subsequently supplied with, e.g. grafted with, carboxylic functionality to serve as the linking group or have carboxylic functionality in the backbone itself (such as an ethylene-co-propylene-co- maleimide copolymer).
• the polymer backbone P is a copolymer of ethylene and an a-olefin, such as propylene and/or butylene.
• Example ethylene-olefin-based polymers include ethylene propylene copolymers.
• the olefin-based polymer is a copolymer where ethylene makes up at least 10 % of the monomer used to prepare the copolymer on a molar basis, or at least 20 mole %, or at least 50 mole %.
• Ethylene-propylene or higher alpha monoolefin copolymers may consist of 15 to 80 mole % ethylene and 20 to 85 mole % propylene or higher monoolefin. In some embodiments, the mole ratio is 30 to 80 mole % ethylene and 20 to 70 mole % of at least one C 3 to Ci 0 alpha monoolefin, for example, 50 to 80 mole % ethylene and 20 to 50 mole % propylene.
• Terpolymer variations of the foregoing polymers may contain up to 15 mole %, or up to 10 mole % of a non-conjugated diene or triene.
• the polymer backbone e.g., the ethylene copolymer or terpolymer
• the polymer can be in forms other than substantially linear, that is, it can be a branched polymer or a star polymer.
• the polymer can also be a random copolymer or a block copolymer, including di- blocks and higher blocks, including tapered blocks and a variety of other structures.
• the polymer backbone (olefin-based polymer) may have a number average molecular weight Mn (measured by gel permeation chromatography, using a polystyrene standard), which can be up to 150,000 or higher, e.g., at least 1 ,000 or at least 3,000 or at least 5,000, such as up to 150,000 or up to 120,000, or up to 100,000, or up to 50,000, or up to 15,000, e.g., about 3,000 to about 15,000.
• Mn number average molecular weight measured by gel permeation chromatography, using a polystyrene standard
• the sulfonated dispersant viscosity modifier may have a number average molecular weight Mn (by gel permeation chromatography, polystyrene standard), which can be up to 150,000 or higher, e.g., at least 2,000 or at least 3,000 or at least 5,000, such as up to 150,000 or up to 120,000, or up to 100,000, or up to 50,000, or up to 18,000, e.g., about 4,000 to about 16,000.
• Mn number average molecular weight
• polymer is used generically to encompass homopolymers, i.e., polymers of a single monomer, as well as copolymers, terpolymers and/or interpolymers. These materials may contain minor amounts of other olefinic monomers so long as their basic characteristics are not materially changed.
• the exemplary sulfonated dispersant viscosity modifier is formed by reacting a carboxylic acid-modified polymer backbone with a hydroxy alkyl amine and/or alkylene polyamine and/or polyol and a hydrocarbyl sulfonate compound.
• the exemplary dispersant viscosity modifier may be formed by reacting a carboxylic acid- modified polymer backbone with an amino-substituted hydrocarbyl sulfonate compound. Where a sulfonic acid is formed, the acid may be converted to its salt through reaction with a suitable base.
• the unsaturated carboxylic acid monomer used to form the linking group X may be derived from maleic acid and/or anhydride. As noted above, this portion of the linking group may be incorporated and/or attached to the polymer backbone during the polymerization of the polymer backbone, for example, by mixing a monomer containing the linking group in with the other monomers used to prepare the polymer backbone. In other embodiments, this part of the linking group may be added by grafting the group onto an already prepared polymer backbone. [0042] As noted above, in some embodiments the unsaturated carboxylic acid used to form the linking group is contained within a monomer copolymerized within the polymer backbone chain. In other embodiments, the unsaturated carboxylic reactant may be present as a pendent group attached by, for example, a grafting process.
• Examples of suitable carboxylic-acid containing polymers which are representative of the polymer backbone described above with carboxylic reactant portion of the liking group attached, include maleic anhydride-ethylene- propylene copolymers, maleic anhydride-styrene copolymers, including partially esterified versions thereof, and copolymers thereof.
• Nitrogen-containing esterified carboxyl-containing interpolymers prepared from maleic anhydride and styrene-containing polymers are described in U.S. Pat. No. 6,544,935 to Vargo et al.
• Other polymer backbones which are used for preparing dispersants may also be used.
• polymers derived from isobutylene and isoprene are described in U.S. Pub. No. 20040034175 to Kolp.
• suitable polymer backbones include substantially hydrogenated copolymers of vinyl aromatic materials such as styrene and unsaturated hydrocarbons such as conjugated dienes, e.g., butadiene or isoprene.
• the olefinic unsaturation is typically substantially completely hydrogenated by known methods, but the aromatic unsaturation may remain.
• Such polymers can include random copolymers, block copolymers, or star copolymers.
• Suitable backbone polymers include styrene- ethylene-alpha olefin polymers, as described in PCT publication WO 2001/030947, and polyacrylates or polymethacrylates, generically called poly(meth)acrylates.
• the (meth)acrylate monomers within the polymer chain itself may serve as the carboxylic acid functionality or reactive equivalent thereof which is used to react with the amine functionality which provides the linker unit Y.
• additional acid functionality may be copolymerized into the (meth)acrylate chain or even grafted onto it, particularly in the case of acrylate polymers.
• the polymer backbone may be prepared from ethylene and propylene or it may be prepared from ethylene and a higher olefin within the range of (C 3 to Ci 0 ) alpha-monoolefins, which may then in either case be grafted with a suitable carboxylic acid-containing monomer, to serve as the linking group X.
• interpolymers More complex polymer backbones, often designated as interpolymers, may also be included. Such materials are generally used to prepare an interpolymer backbone is a polyene monomer selected from conjugated or non- conjugated dienes and trienes.
• the non-conjugated diene component is one having from about 5 to about 14 carbon atoms.
• the diene monomer is characterized by the presence of a vinyl group in its structure and can include cyclic and bicyclo compounds.
• Representative dienes include 1 ,4- hexadiene, 1 ,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1 ,5-heptadiene, and 1 ,6-octadiene.
• a mixture of more than one diene can be used in the preparation of the interpolymer.
• the ethylenically unsaturated carboxylic acid monomer may be grafted onto the polymer backbone in a number of ways, such that a resulting polymer intermediate with linking groups X is characterized by having carboxylic acid acylating functions within its structure.
• Such materials which are attached to the polymer typically contain at least one ethylenic bond (prior to reaction) and at least one, or at least two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into the carboxyl groups by oxidation or hydrolysis.
• Maleic anhydride or an alkyl-substituted derivative thereof (e.g., methyl maleic anhydride or ethyl maleic anhydride) is suitable for forming the linking groups. It grafts onto the ethylene copolymer or terpolymer to give two carboxylic acid functionalities.
• additional unsaturated carboxylic materials include chlormaleic anhydride, itaconic anhydride, and the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, acrylic acid, cinnamic acid, and their esters.
• Example intermediate polymers of this type are available from Mitsui under the tradename LucantTM, such as LucantTMA-5320H polymer.
• the polymer intermediate may then be reacted with the hydroxy alkyl amine, alkylene polyamine, or polyol to provide the intermediate polymer with linker units Y.
• the polymer intermediate is reacted directly with an amine-substituted hydrocarbyl sulfonate compound or other substituted hydrocarbyl sulfonate compound capable of reaction with the intermediate polymer.
• Hydroxy alkyl amines and/or alkylene polyamines suitable for forming linker units Y are not overly limited. In some embodiments, they may be represented by the general formula:
• Suitable hydroxy alkyl amines include amines having at least one amine group and at least one hydroxyl group, where the amine group is a primary, secondary, or tertiary amine group.
• the hydroxy alkyl amines may have 2 to 30 carbon atoms.
• Example hydroxy alkyl amines may include mono-, di- and tri-alkoxylates of ammonia such as mono- and di- and tri-ethanolamine, hydroxy-containing monoamines such as a diethoxylated C 16 to Ci 8 tallowamine, and hydroxy-containing polyamines such as 2-(2-aminoethylamino)ethanol.
• the hydroxy alkyl amine includes 3-hydroxypropyl amine.
• Suitable polyamines for forming linker units Y may have from 2 to 30 carbon atoms.
• Example polyamines include alkylenediamines, N-alkyl alkylenediamines, and polyalkylenepolyamines.
• Useful polyamines include ethylenediamine, 1 ,2-diaminopropane, N-methylethylenediamine, N-tallow(Ci6- Cie)-1 ,3-propylenediamine, N-oleyl-1 ,3-propylenediamine, polyethylenepolyamines such as diethylenetriamine and triethylenetetramine and tetraethylenepentamine and polyethylenepolyamine bottoms.
• Suitable polyols for forming linker units Y are not overly limited. In some embodiments, they may be represented by the general formula:
• R 9 is hydrocarbyl group, and in some embodiments an alkylene group, containing from 1 to 10 carbon atoms.
• the sulfonated dispersant viscosity modifier is prepared using an alkylene diol, an amino- polyol, or combinations thereof.
• suitable diols include butanediol, hexanediol, 2-amino-2-hydroxymethyl-propane-1 ,3-diol, and combinations thereof.
• reaction product of the olefin-based polymer backbone containing the unsaturated carboxylic reactant and the hydroxy alkyl amine and/or alkylene polyamine and/or polyol may then be reacted with the hydrocarbyl sulfonate compound to provide the dispersant viscosity modifier.
• the sulfonated dispersant viscosity modifier is the reaction product of (i) an olefin-based polymer, for example an ethylene propylene copolymer, that has been functionalized with a unsaturated carboxylic reactant, for example, by using maleic anhydride, and (ii) a hydroxy alkyl amine and/or an alkylene polyamine, for example, a hydroxy alkyl amine such as 3- hydroxypropylamine.
• the resulting intermediate can then be reacted with a hydrocarbyl sulfonate compound (which may thereafter be converted to a salt) to provide a dispersant viscosity modifier.
• the sulfonated dispersant viscosity modifier is the reaction product of (i) an olefin-based polymer, for example an ethylene propylene copolymer, that has been functionalized with a unsaturated carboxylic reactant, for example, by using maleic anhydride, and (ii) an amine-substituted hydrocarbyl sulfonate compound (which may thereafter be converted to a salt by reaction with a base) to provide a dispersant viscosity modifier.
• an olefin-based polymer for example an ethylene propylene copolymer
• a unsaturated carboxylic reactant for example, by using maleic anhydride
• an amine-substituted hydrocarbyl sulfonate compound which may thereafter be converted to a salt by reaction with a base
• Suitable hydrocarbyl sulfonate compounds for forming the pendent functional groups are of the general form: B-A-SO 3 M
• A represents a hydrocarbyl group or a substituted hydrocarbyl group
• M is a cation as described above
• B represents a functional group capable of reacting with the linker unit Y, or capable of undergoing direct acyiation with the linking group X.
• B can be NH 2 (giving an amine-substituted hydrocarbyl sulfonate compound, H 2 N-A-SO 3 M) or OH.
• the hydrocarbyl sulfonate compounds can also be in the form of a ring capable of reaction with water to form B-A-SO 3 H.
• the hydrocarbyl group A may be at least 3 carbons in length and may be selected from C3-C 2 0 alkyl groups and C 6 -C 24 aryl or alkylaryl groups, as discussed for R 2 above.
• M may represent a monovalent cation.
• group B is capable of acyiation by the linking group, the linker unit can be omitted, although it may still be useful for chain extension to space the lipophilic sulfonate moiety further from the backbone.
• Example alkyl hydrocarbyl sulfonate compounds suitable for forming the pendent functional groups include aliphatic sulfonic acids represented by formula (IV):
• B is NH 2 or OH
• R 1 and R 12 are independently H or a Ci to C30 alkyl group.
• pane-1 -sulfonic acid examples include pane-1 -sulfonic acid
• substituted alkyl sulfonate compounds include homocysteic acid:
• Example cyclic sulfonic acids known as sultones which have sulfonyl-oxy group -OSO 2 - in a ri nted by formula (V):
• d is from 1 -10, such as 1 or 2, and
• R 13 , R 14 , and R 15 are independently H or a Ci to C30 alkyl group.
• Useful sultones include, for example, 1 ,3-propanesultone (d 13
• 1 ,3-propanesultone yields products with a terminal -CH 2 -CH 2 -CH 2 -SO 3 H group and 1 ,4- butanesultone yields products with a terminal -CH 2 -CH 2 -CH 2 -SO 3 H group, where the terminal H can subsequently be converted to another cation M as described above.
• aryl sulfonate compounds include those of general formulas (VI), (VII), (VIII), (IX and (X):
• R 16 , R 17 , R 18 , and R 19 are independently selected from H, OH, NH 2 , C-1 -C30 (or C1-C10) alkyl groups, and alkoxy groups,
• R 20 is H or a Ci-C 30 (or C1-C10) alkyl group
• e is at least 1 , such as 1 -20 or 1 -10,
• the NH 2 group may be positioned ortho, meta, or para to the sulfonic acid group.
• Additional substituents e.g., just one, can be positioned on the ring in the locations not occupied by the amine or sulfonic acid.
• the substituent is a methyl group, but can also be a hydroxy (-OH) group, an alkoxy (-OR) group, a nitroxy (-NO 2 ) group, or another amine.
• aryl sulfonate compounds according to formula (VI) include p-aminobenzenesulfonic acid (sulfanilic acid):
• the aryl group can be based on naphthalene.
• the sulfonic acid may occupy either the 1 or 2 position on the ring and the amine may be either on the same ring or on the adjoining ring.
• Substituents can be the same noted for single ring aryl groups and may occupy any sites not occupied by the amine or sulfonic acid.
• aryl sulfonate compounds according to formula (IX) include 7-amino-1 ,3-naphthene disulfonic acid:
• aryl sulfonate compounds according to formula (X) include 8-(2-aminoethylamino -1 -naphthene sulfonic acid:
• the resulting molecule includes a sulfonate moiety which is a sulfonic acid
• it can be subsequently converted to the salt by reaction with a suitable base.
• bases for conversion of the acid form of the sulfonate moiety to the respective sulfonate salt include metal hydroxides, such as NaOH, KOH, and Ca(OH) 2 , and alkyl amines, such as di- or tri-alkyl amines of the general form NR 3 R 4 R 5 , where R 3 , R 4 , and R 5 are as described above.
• the alkyl amine may have alkyl groups having 1 to 30, or 2 to 20, or 3 to 10 carbon atoms.
• dialkyl amines examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, di-(2- ethylhexyl)amine, di-decylamine, di-dodecylamine, di-stearylamine, di- oleylamine, di-eicosylamine, and mixtures thereof.
• trialkyi amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri-(2-ethylhexyl)amine, tri-decylamine, tri- dodecylamine, tri-stearylamine, tri-oleylamine, tri-eicosylamine, and mixtures thereof.
• the reaction can be carried out in a suitable solvent, such as a diluent oil and/or toluene, at a sufficient temperature, such as at least 90°C or at least 100°C, but below the boiling point of the solvent or the decomposition temperature of the product.
• a suitable solvent such as a diluent oil and/or toluene
• the reaction can be accomplished in the substantial absence of solvent, e.g., in a twin screw extruder, Banbury mixer, or similar device.
• the sulfonated dispersant viscosity modifier may be present in the lubricating composition at a concentration of at least 0.05 weight %, such as at least 0.1 weight %, or at least 0.2 weight %, or at least 0.5 weight %.
• the sulfonated dispersant viscosity modifier may be present in the lubricating composition at a concentration of up to 10 weight %, such as up to 5 weight %, or up to 3 weight %, or up to 2.3 weight %.
• HLB values reported herein are determined by the Griffin Method (see Griffin, William C. (1949), “Classification of Surface-Active Agents by 'HLB'", Journal of the Society of Cosmetic Chemists 1 (5): 311 -26 and Griffin, William C. (1954), "Calculation of HLB Values of Non-Ionic Surfactants", Journal of the Society of Cosmetic Chemists 5 (4): 249-56
• HLB 20 * lv M, where Mh is the molecular mass of the hydrophilic portion of the molecule and M is the molecular mass of the whole molecule. This method covers a range from 0-20.
• the exemplary sulfonated dispersant viscosity modifier may have an HLB value according to the Griffin method, of 1 -10, or at least 2, or at least 2.5, or at least 3, and can be up to 9 or up to 8, or up to 7.
• a sulfonated dispersant viscosity modifier with an ethylene propylene backbone having about 240 CH 2 /CH/CH 3 groups has an molecular mass of approximately 3525, as determined by vapor phase osmometry (VPO).
• VPO vapor phase osmometry
• each polymer backbone chain has, on average, 3.5 sites which can be functionalized with the sulfonate moiety.
• 3- aminopropanol (as a linker unit), and sulfanilic acid or butane sultone this provides a head group of the form:
• the HLB for the dispersant viscosity modifier composed of an ethylenepropylene copolymer with aryl sulfonic acid pendent groups can be computed as 4.0.
• the HLB range can be up to about 6.8 or higher for the alkyl sulfonic acid and up to about 6.2 for the aryl sulfonic acid dispersion viscosity modifiers.
• the entire head group is considered as the hydrophilic portion, even though it contains some hydrocarbon portions.
• the exemplary lubricating composition includes an oil of lubricating viscosity.
• Suitable oils include both natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
• Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
• Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
• Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
• Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
• Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
• animal oils e.g., castor oil
• mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
• Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l -hexenes), poly(1 - octenes), trimers or oligomers of 1 -decene, e.g., poly(l -decenes), such materials being often referred to as poly a-olefins, and mixtures thereof; alkyl- benzenes (e.g., dodecylbenzenes, tetra-decylbenzenes, dinonylbenzenes, di-(2- ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkyl al
• Other synthetic lubricating oils include polyol esters (such as Priolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
• Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized 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.
• the base oil may be selected from any of the base oils in Groups l-V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines, namely
• PAOs polyalphaolefins
• Groups I, II and III are mineral oil base stocks. 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”. In one embodiment, the oil of lubricating viscosity may be an API Group II or Group III oil. In another embodiment, the oil of lubricating viscosity may be an API Group I oil.
• the oil of lubricating viscosity may have a kinematic viscosity of less than 15 mm 2 /s (cSt) at 100 °C, and in other embodiments 1 -12 or 2-10 or 3-8 or 4-6 mm 2 /s.
• Kinematic viscosity is determined by ASTM D445-14, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," ASTM International, West Conshohocken, PA, 2003, DOI: 10.1520/D0445-14.
• the dispersant viscosity modifier may have a kinematic viscosity at 100 °C of at least 35 mm 2 /s, or at least 100 mm 2 /s, or at least 500 mm 2 /s.
• 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 sulfonated dispersant viscosity modifier and the other performance additives.
• the oil of lubricating viscosity may be present in the lubricating composition at a concentration of at least 10 wt %, or at least 20 wt %, or at least 40 wt %, or at least 80 wt %, and may be up to 99 wt %, or up to 95 wt %, or up to 90 wt %.
• the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition (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 composition (comprising the additives disclosed herein) is in the form of a finished lubricant, the ratio of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99.9 to 50:50 by weight, or 1 :99 to 30:70 by weight. Additional Performance Additives
• the lubricating composition optionally includes one or more additional performance additives.
• additional performance additives may include one or more metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers (other than the exemplary compound), extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, antiwear agents, and any combination or mixture thereof.
• fully- formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.
• the lubricating composition further includes a dispersant, an antiwear agent, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent, or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
• the lubricating composition further includes a polyisobutylene succinimide dispersant, an antiwear agent, a friction modifier, a viscosity modifier (typically an olefin copolymer such as an ethylene-propylene copolymer), an antioxidant (including phenolic and aminic antioxidants), an overbased detergent (including overbased sulfonates and phenates), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
• a polyisobutylene succinimide dispersant typically an antiwear agent, a friction modifier, a viscosity modifier (typically an olefin copolymer such as an ethylene-propylene copolymer), an antioxidant (including phenolic and aminic antioxidants), an overbased detergent (including overbased sulfonates and phenates), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
• the lubricating composition further includes an antiwear agent such as a metal dihydrocarbyl dithiophosphate (typically zinc dialkyldithiophosphate), wherein the metal dihydrocarbyl dithiophosphate contributes at least 100 ppm, or at least 200 ppm, or 200 ppm to 1000 ppm, or 300 ppm to 800 ppm, or 400 ppm to 600 ppm of phosphorus to the lubricating composition.
• the lubricating composition is free of or substantially free of zinc dialkyldithiophosphate (ZDDP).
• the lubricating composition further includes a dispersant.
• the dispersant may be present at a concentration of 0 wt % to 20 wt %, such as at least 0.01 wt %, or at least 0.1 wt %, or at least 0.1 wt %, or at least 1 wt %, or up to 20 wt %, or up to 15 wt %, or up to 10 wt %, or up to 6 wt % of the lubricating composition.
• the dispersant may be present in the composition at a concentration of 0.2 wt % to 2 wt %.
• Suitable dispersants for use in the exemplary lubricating compositions include succinimide dispersants.
• the dispersant may be present as a single dispersant.
• the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
• the succinimide dispersant may be a derivative of an aliphatic polyamine, or mixtures thereof.
• the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
• the aliphatic polyamine may be ethylenepolyamine.
• the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
• the dispersant may be a N-substituted long chain alkenyl succinimide.
• N-substituted long chain alkenyl succinimides include polyisobutylene succinimide.
• the polyisobutylene from which a polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
• Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. Nos.
• the dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. [0099] In one embodiment, the lubricating composition further includes a dispersant viscosity modifier other than the sulfonated dispersant viscosity modifier described herein.
• the additional dispersant viscosity modifier may be present at a concentration of 0 wt % to 5 wt %, such as at least 0.01 wt %, or at least 0.05 wt %, or up to 5 wt %, or up to 4 wt %, or up to 2 wt % of the lubricating composition.
• Suitable dispersant viscosity modifiers 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, and esterified styrene-maleic anhydride copolymers reacted with an amine.
• acylating agent such as maleic anhydride and an amine
• Exemplary dispersant viscosity modifiers are disclosed, for example, in WO2006/015130 and U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825.
• the lubricating composition further includes a phosphorus-containing antiwear agent.
• the antiwear agent may be present at a concentration of 0 wt % to 3 wt %, such as at least 0.1 wt %, or at least 0.5 wt %, or up to 3 wt %, or up to 1.5 wt %, or up to 0.9 wt % of the lubricating composition.
• the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, or mixture thereof.
• the lubricating composition further includes a molybdenum compound.
• 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.
• the molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
• the lubricating composition further includes an overbased detergent.
• the overbased detergent may be present at 0 wt % to 15 wt %, or at least 0.1 wt %, or at least 0.2 wt %, or at least 0.2 wt %, or up to 15 wt %, or up to 10 wt %, or up to 8 wt %, or up to 3 wt % of the lubricating composition.
• the detergent may be present at 2 wt % to 3 wt % of the lubricating composition.
• the detergent may be present at 0.2 wt % to 1 wt % of the lubricating composition.
• the overbased detergent may be selected from the group consisting of non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof.
• the overbased detergent 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 U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281 ,179.
• phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, as described; for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281 ,179.
• the hybrid detergent can be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
• Suitable overbased detergents are sodium salts, calcium salts, magnesium salts, or mixtures of the phenates, sulfur containing phenates, sulfonates, salixarates and salicylates.
• Overbased phenates and salicylates may have a total base number of 180 to 450 TBN.
• Overbased sulfonates may have a total base number of 250 to 600, or 300 to 500.
• the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described, for example, in U.S. Pub. No. 20050065045.
• the linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
• the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3, or 4 position of the linear chain, and in some instances, predominantly in the 2 position, resulting in the linear alkylbenzene sulfonate detergent.
• the lubricating composition includes an antioxidant, or mixture of antioxidants.
• the antioxidant may be present at 0 wt % to 15 wt 5, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt % of the lubricating composition.
• Antioxidants include sulfurized olefins, alkylated diarylamines (typically alkylated phenyl naphthyl amines for example those commercially available as Irganox® L 06 from CIBA, or alkylated diphenylamines such as dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine), hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), or mixtures thereof.
• alkylated diarylamines typically alkylated phenyl naphthyl amines for example those commercially available as Irganox® L 06 from CIBA
• alkylated diphenylamines such as dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine
• hindered phenols such as molybdenum dithiocarbamates
• the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a steric 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.
• hindered phenol antioxidants examples 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, or 4-dodecyl-2,6-di-tert- butylphenol.
• the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in U.S. Patent 6,559,105.
• the lubricating composition further includes a friction modifier.
• the friction modifier may be present at 0 wt % to 6 wt %, such as at least 0.05 wt %, or at least 0.1 wt %, or up to 6 wt %, or up to 4 wt %, or up to 2 wt % of the lubricating composition.
• the friction modifier is present in the composition at 0.1 to 1.0 wt %.
• friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.
• fatty as used herein, can mean having a Cs to C22 linear alkyl group.
• Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
• the friction modifier may be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
• the friction modifier may be a long chain fatty acid ester.
• the long chain fatty acid ester may be a mono- ester or a diester or a mixture thereof, and in another embodiment the long chain fatty acid ester may be a triglyceride.
• corrosion inhibitors include those described in U.S. Pub. No. 20050038319, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
• the corrosion inhibitors include a Synalox® corrosion inhibitor.
• the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
• Synalox® corrosion inhibitors are described in a product brochure, Form No. 118-01453-0702 AMS, entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications," published by The Dow Chemical Company.
• Metal deactivators including derivatives of benzotriazoles (such as tolyltriazole), dimercaptothiadiazole derivatives, 1 ,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be useful.
• pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, and polyacrylamides.
• the lubricating composition may have a composition as described in Table 1 :
• the sulfonated dispersant viscosity modifier may be present in embodiments (D) at 0.1 to 8 wt %, or (E) 1 to 7 wt %, or (F) 2 to 6 wt %, or (G) 0.1 to 2 wt %, or (H) 0.3 to 1.2 wt % of the lubricating composition, with the amount of dispersant, overbased detergent, antioxidant, antiwear agent, friction modifier, viscosity modifier, any other performance additive and an oil of lubricating viscosity in amounts shown in the table above for embodiments (A) to (C).
• a method of lubricating an internal combustion engine includes supplying to the internal combustion engine a lubricating composition as disclosed herein. Generally, the lubricating composition is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine, during its operation, that require lubrication.
• a use of the dispersant viscosity modifier described herein to improve film thickness and/or antiwear performance of a lubricating composition is provided. These improvements can be considered in addition to the dispersancy and viscosity control performance expected from a dispersant viscosity modifier.
• the lubricating compositions described above may be utilized in an internal combustion engine.
• the engine components may have a surface of steel or aluminum (typically a surface of steel), and may also be coated for example, with a diamond like carbon (DLC) coating.
• An aluminum surface may comprise an aluminum alloy that may be a eutectic or 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 formed of an aluminum alloy or aluminum composite.
• the internal combustion engine may or may not have an Exhaust Gas Recirculation system.
• the internal combustion engine may be fitted with an emission control system or a turbocharger.
• Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
• the internal combustion engine may be a diesel fuelled engine (such as a heavy duty diesel engine), a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine.
• the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
• the internal combustion engine may be a biodiesel fuelled engine.
• the internal combustion engine may be a 2-stroke or 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low- load diesel engines, and automobile and truck engines.
• the internal combustion engine is a gasoline direct injection (GDI) engine.
• GDI gasoline direct injection
• the internal combustion engine is distinct from gas turbine.
• gas turbine which may also be referred to as a jet engine
• gas turbine it is a continuous combustion process that generates a rotational torque continuously without translation and can also develop thrust at the exhaust outlet.
• the lubricating composition for an internal combustion engine may be suitable for use as an engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D874) content.
• the sulfur content of the lubricating composition which is particularly suited to use as an 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.
• the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
• the total sulfated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.4 wt % or less.
• the sulfated ash content may be 0.05 wt % to 0.9 wt %, or 0.1 wt % to 0.2 wt % or to 0.45 wt %.
• 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 0.1 wt % or less, (iii) a sulfated ash content of 1.5 wt % or less, or combinations thereof.
• kinematic viscosity is measured at 100°C (KV 10 o), according to the method of ASTM D445 - 12, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)", ASTM International, West Conshohocken, PA, DOI: 10.1520/D0445-12.
• the viscosity index (VI) is determined according to ASTM D2270- 10e1 , "Standard Practice for Calculating Viscosity Index From Kinematic Viscosity at 40 and 100°C," DOI: 10.1520/D2270-10E01.
• the High Temperature/High Shear rate viscosity, HTHS (150°C), of a lubricating composition containing the exemplary dispersant viscosity modifier is determined herein according to the procedure defined in ASTM D4683-10, "Standard Test Method for Measuring Viscosity of New and Used Engine Oils at High Shear Rate and High Temperature by Tapered Bearing Simulator Viscometer at 150°C," ASTM International, West Conshohocken, PA. This test method determines the viscosity of an oil at 150 °C and 1.0 x 10 6 s "1 using a viscometer having a slightly tapered rotor and stator called the Tapered Bearing Simulator (TBS) Viscometer.
• TBS Tapered Bearing Simulator
• a succinimide intermediate is prepared by adding to a 3 L round bottom flask equipped with a mechanical stirrer, thermowell, nitrogen inlet, Dean-Stark trap and Friedrich's condenser, 852.0 grams of a maleated ethylene propylene copolymer, commercially available from Mitusi as LucantTM A-5320H, and 852.0 g of diluent oil. The material is heated to 1 10°C with stirring and nitrogen purge. 25.8 grams of 3-aminopropanol is added to the mixture, resulting in the formation of a gel. Xylenes (54 g) are added to the flask with continued heating resulting in the gel eventually melting after about 20 minutes of agitation.
• the solution is then warmed to 175°C and agitated for 4.0 hours.
• the solution is cooled to 165°C and held an additional 1.5 hours at this temperature.
• the resulting polymer is stripped of solvents under deep vacuum at 165°C for 40 minutes. 1712.0 grams of the succinimide intermediate, appearing as a viscous yellow liquid, is recovered.
• Example 2 Preparation of a Maleated Ethylene Propylene Alkyl Sulfonic Acid Dispersant Viscosity Modifier
• a dispersant viscosity modifier is prepared by adding to a 2 L round bottom flask equipped with a mechanical stirrer, thermowell, nitrogen inlet, Dean-Stark trap and Friedrich's condenser, 300.0 grams of the succinimide intermediate of Example 1 and 328.2 g of diluent oil. The solution is heated to 110°C with agitation and nitrogen purge. Then, 1 1.1 grams of butanesultone are added, followed by toluene (50 ml). The solution is agitated at 125°C for 2 hours, then the temperature increased to 150°C for 6 hours. Solvent is then removed under deep vacuum at 150°C for 30 min to yield 625.0 grams of product, appearing as a viscous liquid. The resulting dispersant viscosity modifier is referred to below as 3.5% MAA alkyl sulfonic acid.
• a dispersant viscosity modifier is prepared by adding to a 2 L round bottom flask equipped with a mechanical stirrer, thermowell, nitrogen inlet, Dean-Stark trap and Friedrich's condenser, 430.0 grams of maleated ethylene propylene copolymer (LucantTM A-5320H) and 486.0 g of diluent oil. The solution is heated to 120°C with agitation and nitrogen purge for 1 hour. 31.7 grams of tributylamine is added to the flask followed by 27.2 grams of sulfanilic acid. The flask is heated to 160°C for 7.5 hours. Additional tributylamine (31.7 g) is added to the flask with agitation at 160°C for 6.75 hours.
• Example 3 Excess tributylamine is removed under deep vacuum at 160°C for 3 hours. 546.8 g of diluent oil is added to the flask, providing 1430.3 g of product as a dark viscous liquid. The resulting dispersant viscosity modifier is referred to below as 3.5% MAA aryl tributylammonium sulfonate.
• the product of Example 3 may be washed with aqueous acid to facilitate a cation exchange from a triaikylammonium ion to an H + ion, effectively converting the salt to an acid, as described in Example 4.
• Example 4 Preparation of a Maleated Ethylene Propylene Aryl Sulfonic Acid Dispersant Viscosity Modifier
• a dispersant viscosity modifier is prepared by adding to a 5 L round bottom flask equipped with a mechanical stirrer, thermowell, nitrogen inlet,
• a 1 N solution of H 2 S0 4 is prepared and charged (274.5 ml) to the flask. Contents of the flask are stirred for 20 min at 40 °C. Flask contents are transferred to a separatory funnel and the phases allowed to separate. The aqueous phase is removed and the organic phase is returned to the flask.
• a 2 N solution of H 2 S0 4 is prepared and charged (137.3 ml) to the flask. Contents of the flask are stirred for 20 min at 40°C. Contents of the flask are transferred to a separatory funnel and the phases allowed to separate. The aqueous phase is removed and the organic phase is returned to the flask.
• 2 N H 2 S0 4 (137.3 ml) is charged a second time to the flask. Contents of the flask are stirred for 20 min at 40°C. Contents of the flask are transferred to a separatory funnel and the phases allowed to separate. The aqueous phase is removed and the organic phase is returned to the flask. 2 N H 2 S0 (137.3 ml) is again charged to the flask. Contents of the flask are stirred for 20 min at 40°C. Contents of the flask are transferred to a separatory funnel and the phases allowed to separate. The aqueous phase is removed and the organic phase is returned to the flask.
• the contents of the flask are heated to 120°C resulting in the collection of water and toluene.
• the temperature is increased to 135°C and held, resulting in the collection of additional toluene.
• the temperature is increased to 150°C and held, resulting in the collection of additional toluene.
• Vacuum is applied to -250 mmHg at 150°C, resulting in the collection of toluene. Vacuum is further applied to 10-15 mmHg at 150°C, resulting in the collection of additional toluene. Vacuum is released and the product is filtered. The resulting product is a dark viscous oil.
• the dispersant viscosity modifier of Example 2 is prepared at 25 wt% polymer in 75 wt% diluent oil. This is blended into a group III base oil in amounts by weight to form lubricating compositions, as summarized in Table 2 below.
• Comparative Example 5 includes an amine-free dispersant viscosity modifier (a polymethacrylate (84% C12-15 methacrylate/16% methyl methacrylate), with a weight average molecular weight of 330,000).
• Examples 6 and 7 contain the dispersant viscosity modifiers of Examples 2 and 4 respectively as well as some of the amine-free dispersant viscosity modifier used in Example 5.
• each of the blends is designed to have nearly equivalent kinematic viscosities at 100°C (KV 0 o) to allow for direct comparison:
• the data in parenthesis is the amount of actives for each component.
• the weight % actives are based on the entire composition.
• the Dispersant- lnhibitor Package may include some oil.
• the lubricating compositions of Examples 5-7 include about 0.75% zinc dialkyldithiophosphate (ZDDP) (which delivers about 0.076% phosphorus to the lubricating composition).
• Friction properties were determined using a Mini Traction Machine (MTM). The lubricants are evaluated in a commercially-available mini-traction tester machine. A simulated concentrated contact forms between a steel ball and a steel disc (Smooth disk). Traction measurements are made at a rolling speed (of the steel ball) of 2.5 m/s and a 20% slide to roll ratio. The temperature was 140 °C and load was 72N. FIGURE 1 shows the Stribeck curve obtained.
• MTM Mini Traction Machine
• the performance of the 3.5% MAA alkyl sulfonic acid in the finished fluid can be measured in all three regions of the Stribeck curve.
• the area of interest is the mixed regime, which can be found between the two vertical lines.
• the mixed regime is indicative of the durability of the friction modifier characteristics of the dispersant viscosity modifier, as determined by the Sequence VID engine test (ASTM D7589), which is heavily weighted towards the mixed regime.
• comparative Example 8 includes a conventional dispersant viscosity modifier (32 wt % active polymer, 68 wt % oil).
• this replaced with either 3.5% MAA alkyl sulfonic acid (prepared at 25 wt % polymer, 75 wt % oil) or 3.5% MAA aryl tributylammonium sulfonate (prepared at 29.7 wt % polymer, 70.3 wt % oil) at a treat rate to obtain the following viscometric parameters:
• the weight % actives are also based on the entire composition.
• the lubricating compositions of Examples 8-10 include about 1 % zinc dialkyldithiophosphate (ZDDP) (which delivers about 0.1 1 % phosphorus to the composition).
• ZDDP zinc dialkyldithiophosphate
• the compositions include about 1 % sulfated ash and have a TBN of about 8.5.
• the film thickness of the blends in TABLE 3, when subjected to boundary, mixed and hydrodynamic lubrication conditions is measured by an elastohydrodynamic (EHD) ball on plate rig. Briefly, a chamber is flooded with one of the blends from TABLE 3. The chamber is equipped with a ball that rolls on a glass plate and a chromium spacer.
• EHD elastohydrodynamic
• the film thickness is measured to the nanometer scale.
• the experiment is performed at 140°C over a variety of rolling speeds. Conditions are as follows: 0.5 GPa Hertz Pressure, 17 N.
• FIGURE 2 shows the EHD data obtained. It can be seen that the Example 9 and 10 NOCH-S DVMs both form a thicker film, as compared to comparative Example 8.

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