EP2723836A1 - Schmierzusammensetzung mit einem dispergiermittel - Google Patents

Schmierzusammensetzung mit einem dispergiermittel

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Publication number
EP2723836A1
EP2723836A1 EP12730740.3A EP12730740A EP2723836A1 EP 2723836 A1 EP2723836 A1 EP 2723836A1 EP 12730740 A EP12730740 A EP 12730740A EP 2723836 A1 EP2723836 A1 EP 2723836A1
Authority
EP
European Patent Office
Prior art keywords
acid
lubricating composition
dispersant
carbon atoms
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12730740.3A
Other languages
English (en)
French (fr)
Other versions
EP2723836B1 (de
Inventor
Matthew D. Gieselman
Joanne L. Jones
David J. Moreton
Dean Thetford
Hannah Greenfield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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Publication date
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Publication of EP2723836A1 publication Critical patent/EP2723836A1/de
Application granted granted Critical
Publication of EP2723836B1 publication Critical patent/EP2723836B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • 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

Definitions

  • the invention provides a lubricating composition containing a lubricating composition comprising an oil of lubricating viscosity and a quaternised polyester salt.
  • the invention further relates to a method of lubricating a mechanical device (such as an internal combustion engine) with the lubricating composition.
  • the invention further relates to the use of the quaternised polyester salt as a dispersant.
  • the objectives of the present invention include providing at least one of (i) dispersancy, (ii) cleanliness, or (iii) a lubricant with reduced sludge formation.
  • the present invention provides a lubricating composition comprising :
  • a quaternised polyester salt which comprises a product obtained/obtainable by reaction of (i) a polyester containing a tertiary amino group; and (ii) a quaternising agent suitable for converting the tertiary amino group to a quaternary nitrogen, wherein the quaternising agent is selected from the group consisting of a dialkyl sulphate, a benzyl halide, an organic carbonate; an organic epoxide in combination with an acid or mixtures thereof; and
  • a dispersant typically a succinimide dispersant
  • the present invention provides a lubricating composition
  • a lubricating composition comprising: an oil of lubricating viscosity
  • a quaternised polyester salt which comprises a product obtained/obtainable by reaction of (i) a polyester containing a tertiary amino group; and (ii) a quaternising agent suitable for converting the tertiary amino group to a quaternary nitrogen, wherein the quaternising agent is selected from the group consisting of a dialkyl sulphate, a benzyl halide, an organic carbonate, an ester of a polycarboxylic acid, an organic epoxide in combination with an acid, and mixtures thereof; and
  • a dispersant typically a succinimide dispersant
  • the invention provides for a method of lubricating a mechanical device with a lubricating composition disclosed herein.
  • the mechanical device may be an internal combustion engine.
  • the internal combustion engine may have a steel surface on at least one of a cylinder bore, cylinder block, or piston ring.
  • the internal combustion engine may have an aluminium alloy, or aluminium composite surface on at least one of a cylinder bore, cylinder block, or piston ring.
  • the present invention provides a detergent, a process to prepare a detergent, a lubricating composition, a method for lubricating a mechanical device and a use as disclosed above.
  • the polyester quaternary salt of the invention includes quaternised polyester amine, amide, and ester salts.
  • the additives may also be described as quaternary polyester salts.
  • the additives of the invention may be described as the reaction product of: a polyester containing a tertiary amino group; and a quaternising agent suitable for converting the tertiary amino group to a quaternary nitrogen.
  • the quaternising agent may be selected from the group consisting of a dialkyl sulphate, a benzyl halide, an organic carbonate, an ester of a polycarboxylic acid, an organic epoxide in combination with an acid, and mixtures thereof.
  • the polyester containing a tertiary amino group used in the preparation of the additives of the invention may also be described as a non- quaternised polyester containing a tertiary amino group.
  • fatty carboxylic acid used in relation to the polyester means an acid with a carbon chain of 8 to 22, or 10 to 22 carbon atoms.
  • the polyester may be a reaction product of a fatty carboxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group.
  • the reaction product may be formed by adding the fatty carboxylic acid and the compound having an oxygen or nitrogen atom capable of condensing with said acid in any order.
  • Suitable fatty carboxylic acids that may used in the preparation of the polyesters described above may be represented by the formula:
  • R 1 may be a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R may be a hydrocarbylene group containing from 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms present
  • R 1 2 1 from R and R may be 6 or more, or 8 or more.
  • R contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms
  • R may contain from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms.
  • the fatty carboxylic acid used in the preparation of the polyester may be 12-hydroxystearic acid, ricinoleic acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic acid, 5-hydroxy decanoic acid, 4- hydroxy decanoic acid, 10-hydroxy undecanoic acid, or combinations thereof.
  • nitrogen or oxygen containing compounds capable of condensing with the acylating agents, which also have a tertiary amino group, or compounds that may be alkylated into such compounds include: 1- aminopiperidine, l -(2-aminoethyl)piperidine, l -(3-aminopropyl)-2-pipecoline, 1- methyl-(4-methylamino)piperidine, 4-(l -pyrrolidinyl)piperidine, 1 -(2-amino- ethyl)pyrrolidine, 2-(2-aminoethyl)- 1 -methylpyrrolidine, N,N-diethylethylene- diamine, N,N-dimethylethylenediamine, ⁇ , ⁇ -dibutylethylenediamine, N,N- di ethyl -1 ,3- diaminoprop ane , N ,N - dimethyl - 1 , 3 - di aminoprop ane , N ,N
  • the nitrogen or oxygen containing compounds may further include aminoalkyl substituted heterocyclic compounds such as l -(3- aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.
  • alkanolamines including but not limited to triethanolamine, ⁇ , ⁇ -dimethylaminopropanol, N,N-di ethyl - aminopropanol, ⁇ , ⁇ -diethylaminobutanol, triisopropanolamine, l -[2-hydroxy- ethyljpiperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanol amine, N-butyldiethanolamine, N,N-diethylaminoethanol, ⁇ , ⁇ -dimethyl aminoethanol, 2-dimethylamino-2-methyl- l-propanol.
  • the resulting additive includes a
  • the nitrogen or oxygen containing compound may be triisopropanolamine, l -[2-hydroxyethyl]piperidine, 2 -[2 -(dimethyl amino) ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N- butyldiethanolamine, ⁇ , ⁇ -diethylaminoethanol, N,N-dimethylaminoethanol, 2- dimethylamino-2-methyl-l -propanol, or combinations thereof.
  • the compound having an oxygen or nitrogen atom capable of condensing with said acid and further having a tertiary amino group comprises ⁇ , ⁇ -diethylethylenediamine, N,N-dimethylethylenediamine,
  • the quaternised polyester salt may be a quaternised polyester amide salt.
  • the polyester containing a tertiary amino group used to prepare the quaternised polyester salt may be a polyester amide containing a tertiary amino group.
  • the amine or aminoalcohol may be reacted with a monomer and then the resulting material may be polymerised with additional monomer, resulting in the desired polyester amide which may then be quaternised.
  • the quaternised polyester salt includes an cation represented by the following formula:
  • the quaternised polyester salt may be capped with a C I -22, or a C8-20, fatty acid.
  • suitable acids include oleic acid, palmitic acid, stearic acid, erucic acid, lauric acid, 2-ethylhexanoic acid,
  • the number average molecular weight (Mn) of the quaternised polyester salts of the invention may be from 500 to 3000, or from 700 to 2500.
  • the polyester useful in the present invention may be obtained/obtainable by heating one or more hydroxycarboxylic acids or a mixture of the hydroxycarboxylic acid and a carboxylic acid, optionally in the presence of an esterification catalyst.
  • the hydroxycarboxylic acids may, in certain embodiments, have the formula HO-X-COOH wherein X may be a divalent saturated or unsaturated aliphatic radical containing at least 8 carbon atoms and in which there are at least 4 carbon atoms between the hydroxy and carboxylic acid groups, or from a mixture of such a hydroxycarboxylic acid and a carboxylic acid which is free from hydroxy groups.
  • This reaction may be carried out at a temperature in the region of 160 °C to 200 °C , until the desired molecular weight has been obtained.
  • the course of the esterification may be followed by measuring the acid value of the product, with the desired polyester, in some embodiments, having an acid value in the range of 10 to 100 mg KOH/g or in the range of 20 to 50 mg KOH/g.
  • the indicated acid value range of 10 to 100 mg KOH/g is equivalent to a number average molecular weight range of 5600 to 560.
  • the water formed in the esterification reaction may be removed from the reaction medium, and this may be conveniently done by passing a stream of nitrogen over the reaction mixture or by carrying out the reaction in the presence of a solvent, such as toluene or xylene, and distilling off the water as it is formed.
  • a solvent such as toluene or xylene
  • the resulting polyester may then be isolated in conventional manner; however, when the reaction is carried out in the presence of an organic solvent whose presence would not be harmful in the subsequent application, the resulting solution of the polyester may be used.
  • the radical represented by X may contain from 12 to 20 carbon atoms, optionally where there are between 8 and 14 carbon atoms between the carboxylic acid and hydroxy groups.
  • the hydroxycarboxylic acid may contain a second hydroxy group.
  • the hydroxycarboxylic acid may contain one hydroxy group, and one carboxylic acid group.
  • hydroxycarboxylic acids include ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulphation of oleic acid followed by hydrolysis), and 12-hydroxystearic acid, and especially the commercially available hydrogenated castor oil fatty acid which contains in addition to 12-hydroxystearic acid minor amounts of stearic acid and palmitic acid.
  • the polyester may be derived from commercial 12- hydroxy-stearic acid and may have a number average molecular weight of about
  • Polyesters such as this are described in greater detail in U.K. Patent Specification Nos. 1373660 and 1342746.
  • the components used to prepare the additives described above are substantially free of, essentially free of, or even completely free of, non-polyester-containing hydrocarbyl substituted acylating agents and/or non-polyester-containing hydrocarbyl substituted diacylating agents, such as for example polyisobutylene succinic anhydride.
  • the excluded hydrocarbyl-substituted acylating agent may be a dicarboxylic acylating agent.
  • the excluded hydrocarbyl-substituted acylating agent is polyisobutylene succinic anhydride.
  • the components of the present invention are primarily composed of materials other than hydrocarbyl substituted acylating agents described above such that these agents are not significantly involved in the reaction and the compositions of the invention do not contain significant amounts of additives derived from such agents.
  • the quaternised salt of the present invention are formed when the non- quaternised polyester described above are reacted with a quaternising agent.
  • Suitable quaternising agents include a dialkyl sulphate, a benzyl halide, an organic carbonate; an ester of a polycarboxylic acid, an organic epoxide in combination with an acid, and mixtures thereof.
  • the quaternising agent may include an ester of a polycarboxylic acid.
  • the ester of a polycarboxylic acid is described in international publication WO 2011/095819 (published 1 1 August 201 1).
  • esters are alkyl esters with alkyl groups that contain from 1 to 4 carbon atoms. Suitable examples include diesters of oxalic acid, diesters of phthalic acid, diesters of maleic acid, diesters of malonic acid, diesters of tartaric acid, or diesters or triesters of citric acid.
  • the quaternising agent may be derived from a dialkyl sulphate such as dimethyl sulphate, N-oxides, sultones such as propane and butane sultone; alkyl, acyl or araalkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted carbonates. If the alkyl halide may be benzyl chloride, the aromatic ring may be optionally further substituted with alkyl or alkenyl groups.
  • a dialkyl sulphate such as dimethyl sulphate, N-oxides, sultones such as propane and butane sultone
  • alkyl, acyl or araalkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or
  • the hydrocarbyl (or alkyl) groups of the hydrocarbyl substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group.
  • the hydrocarbyl substituted carbonates contain two hydrocarbyl groups that may be the same or different. Examples of suitable hydrocarbyl substituted carbonates include dimethyl or diethyl carbonate.
  • the quaternising agent may be an organic epoxide, as represented by the following formula, in combination with an acid:
  • R 1 , R 2 , R 3 and R 4 may be independently H or a hydrocarbyl group contain from 1 to 50 carbon atoms.
  • examples of an organic epoxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and combinations thereof. In one embodiment the quaternising agent does not contain styrene oxide.
  • the acid used with the hydrocarbyl epoxide may be a separate component, such as acetic acid.
  • the hydrocarbyl acylating agent may be a dicarboxylic acylating agent
  • the detergent may be prepared by combining reactants which are essentially free of, or even free of, a separate acid component, such as acetic acid, and rely on the acid group of the hydrocarbyl acylating agent instead.
  • a small amount of an acid component may be present, but at ⁇ 0.2 or even ⁇ 0.1 moles of acid per mole of hydrocarbyl acylating agent.
  • the quaternising agent of the invention does not contain any substituent group that contains more than 20 carbon atoms.
  • the long substituent group that allows for the resulting additive to be organic soluble and thus useful for the purposes of this invention is not provided by the quaternising agent but instead is brought to the additive by the non-quaternised polyester having an amine functionality to quaternising agent ratio of 1 :0.1 to 2, or 1 : 1 to 1.5, or 1 : 1 to 1.3.
  • the quaternised polyester salt may be present at 0.1 wt % to 10 wt %, or 1 wt % to 8 wt %, or 2 wt % to 6.5 wt % of the lubricating composition.
  • the lubricating composition may further include a dispersant, or mixtures thereof.
  • 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 invention does include a dispersant 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.
  • the succinimide dispersant may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment the aliphatic polyamine may be ethylenepolyamine.
  • the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide.
  • 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 diamine, typically diethyleneamine).
  • an alcohol such as pentaerythritol
  • an amine such as a diamine, typically diethyleneamine
  • the dispersant may be an N-substituted long chain alkenyl succinimide.
  • An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide.
  • the polyisobutylene from which 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 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,
  • 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 such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • hydrocarbon- substituted succinic anhydrides such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as terephthalic acid
  • nitriles such as tere
  • the dispersant may be borated or non-borated.
  • a borated dispersant may be a succinimide dispersant.
  • the dispersant prepared by a process that includes an "ene” reaction may be a polyisobutylene succinimide having a carbocyclic ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the dispersant molecules.
  • the "ene” reaction may have a reaction temperature of 180 °C to less than 300 °C, or 200 °C to 250 °C, or 200 °C to 220 °C.
  • the dispersant may also be obtained/obtainable from a chlorine- assisted process, often involving Diels-Alder chemistry, leading to formation of carbocyclic linkages.
  • the process is known to a person skilled in the art.
  • the chlorine-assisted process may produce a dispersant that is a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules. Both the thermal and chlorine-assisted processes are described in greater detail in U.S. Patent 7,615,521 , columns 4-5 and preparative examples A and B.
  • the dispersant may have a carbonyl to nitrogen ratio (CO:N ratio) of 5 : 1 to 1 : 10, 2: 1 to 1 : 10, or 2: 1 to 1 :5, or 2: 1 to 1 :2.
  • the dispersant may have a CO:N ratio of 2: 1 to 1 : 10, or 2: 1 to 1 :5, or 2: 1 to 1 :2, or 1 : 1.4 to 1 :0.6.
  • the dispersant may be present at 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.5 wt % to 9 wt %, or 1 wt % to 8.5 wt % of the lubricating composition.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydro cracking, hydro gen ation, and hydro finishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056] (a similar disclosure is provided in US Patent Application 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
  • 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 invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed 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.
  • a lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described herein below).
  • the lubricating composition of the invention optionally comprises other performance additives.
  • the other performance additives include at least one of metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives.
  • the lubricating composition of the invention may further include other additives.
  • the invention provides a lubricating composition further comprising at least one of a dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent, or mixtures thereof.
  • the invention provides a lubricating composition further comprising at least one of a polyisobutylene succinimide dispersant, an antiwear agent, a dispersant viscosity modifier, 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 sulphonates and phenates), or mixtures thereof.
  • a polyisobutylene succinimide dispersant typically an antiwear agent, a dispersant viscosity modifier, 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 sulphonates and phenates), or mixtures thereof.
  • 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 selected from the group consisting of 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.
  • Antioxidants include sulphurised olefins, diarylamines, alkylated diarylamines, hindered phenols, 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-a- 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, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines .
  • 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.
  • 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-butyl- phenol.
  • 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 US Patent 6,559, 105.
  • molybdenum dithiocarbamates which may be used as an antioxidant, include commercial materials sold under the trade names such as
  • Vanlube 822TM and MolyvanTM A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-LubeTM 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 styrene-butadiene 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 International Application WO 2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures thereof.
  • the dispersant viscosity modifier may include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalised with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalised with an amine, or styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Patents 4,863,623; 6, 107,257; 6, 107,258; 6, 1 17,825; and US 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 US 7,790,661 column 2, line 48 to column 10, line 38.
  • the invention provides a lubricating composition further comprising an overbased metal-containing detergent.
  • the metal of the metal-containing detergent may be zinc, sodium, calcium, barium, or magnesium.
  • the metal of the metal-containing detergent may be sodium, calcium, or magnesium.
  • an overbased detergent may be sodium, calcium or magnesium salt of the phenates, sulphur containing phenates, sulphonates, salixarates and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN. Overbased sulphonates typically have a total base number of 250 to 600, or 300 to 500. Overbased detergents are known in the art. In one embodiment the sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919). 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 sulphonate detergent may be particularly useful for assisting in improving fuel economy.
  • the sulphonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulphonate compounds as disclosed in paragraphs [0046] to [0053] of US Patent Application 2008/01 19378.
  • the overbased metal-containing detergent may be a calcium or magnesium an overbased detergent.
  • Overbased detergents are known in the art. Overbased materials, otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterised by a metal content in of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, 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 amount of "excess" metal is commonly expressed in terms of metal ratio.
  • metal ratio is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • 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 overbased detergent (other than the detergent of the present invention) may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %.
  • the detergent may be present at 2 wt % to 3 wt % of the lubricating composition.
  • the detergent may be present at 0.2 wt
  • an engine lubricating composition further comprises at least one overbased detergent with a metal ratio of at least 3, or at least 8, or at least 15.
  • the friction modifier may be selected from the group consisting of 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.
  • 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, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulphurised 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 thio- carbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the antiwear agent may in one embodiment include a tartrate or tartrimide as disclosed in International Publication WO 2006/04441 1 or Canadian Patent CA 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 Patent Application 20050198894.
  • the lubricating composition may further include a phosphorus- containing antiwear agent.
  • a 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
  • Another class of additives includes oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651.
  • the oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • the oil soluble titanium compound is a titanium (IV) alkoxide.
  • the titanium alkoxide is 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 is titanium (IV) isopropoxide.
  • the titanium alkoxide is titanium (IV) 2-ethylhexoxide.
  • the oil soluble titanium compound is a titanium carboxylate.
  • the titanium (IV) carboxylate is titanium neodecanoate.
  • pour point depressants that may be useful in the compositions of the invention 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.
  • 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-37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
  • An engine lubricating composition in different embodiments may have a composition as disclosed in the following table:
  • the invention provides a method of lubricating an internal combustion engine.
  • the engine components may have a surface of steel or aluminium.
  • An aluminium surface may be derived from an aluminium alloy that may be a eutectic or a hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the aluminium surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminium alloy, or aluminium composite.
  • 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 marine diesel engine may be lubricated with a marine diesel cylinder lubricant (typically in a 2-stroke engine), a system oil (typically in a 2-stroke engine), or a crankcase lubricant (typically in a 4-stroke engine).
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
  • the sulphur 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 sulphur 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 0.04 wt % to 0.12 wt %.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the lubricating composition may be an engine oil, wherein the lubricating composition may be characterised as having at least one of (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.12 wt
  • Example 1 A non-quaternised polyester amide is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to sub-line addition pipe, nitrogen line and thermocouple/temperature controller system, 6 moles of 12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where the reaction is carried out at about 130 °C and held for about 4 hours. The reaction mixture is then cooled to about 100 °C and zirconium butoxide is added, in an amount so that the catalyst makes up 0.57 percent by weight of the reaction mixture. The reaction mixture is heated to about 195 °C and held for about 12 hours. The resulting product is cooled and collected.
  • Example 2 A quaternised polyester amide is prepared by placing 511.7 g of Example 1 in a 1L flask with 179 g methanol and 18.1 g acetic acid. The solution is heated with agitation under an atmosphere of nitrogen to 55 °C. 28.2 g propylene oxide is charged sub-surface over 4 h and the solution is stirred at 55 °C for 17 h. 184.5 g diluent oil is added and the vessel is placed under vacuum. The temperature is increased to 70 °C over 2 hours until the methanol is removed. The solution is further diluted with 181.6 g diluent oil and cooled to 60 °C.
  • Example 3 Substantially the same procedure is used as in Example 2 except that styrene oxide is used instead of propylene oxide.
  • the isolated material has a TAN of 5.62 mg KOH/g, a TBN of 25.87 mg KOH/g, 0.73 % N and a kinematic viscosity at 100 °C of 90.9 mm/s.
  • Example 5 is similar to Example 4, except ricinoleic acid is used instead of 12-hydroxystearic acid.
  • Example 6 A mixture of 348 parts of xylene and 3350 parts of a commercial grade of 12-hydroxystearic acid (having acid and hydroxyl values of 182 mg KOH/g. and 160 mg KOH/g. respectively) is stirred for 22 hours at 190 °C to 200 °C, the water formed in the reaction being separated from the xylene in the distillate which is then returned to the reaction medium. After 152 parts of water have been collected, the xylene is removed by heating at 200 °C in a stream of nitrogen. The resulting pale amber coloured liquid has an acid value of 35.0 mg KOH/g. This is polyester B.
  • a mixture of 1600 parts of polyester B and 102 parts of 3- dimethylaminopropylamine is stirred for 2 and a half hours at 160 °C under a reflux condenser and in a current of nitrogen. 10 Parts by volume of the mixture are then distilled off; the temperature is raised to 190 °C during 20 minutes, and maintained at 190 °C to 200 °C for 2 hours 45 minutes. The resulting pale amber coloured viscous liquid partially solidifies on cooling to ambient temperature.
  • the product is then heated to 44 °C and 183 parts of dimethyl sulphate is added. The temperature increased to 72 °C. The mixture is then heated to 90 °C to 100 °C and held for 90 minutes. The product is a pale amber coloured viscous liquid which forms a gum on cooling
  • Example 7 is similar to Example 6, except ricinoleic acid is used instead of 12-hydroxystearic acid.
  • Example 8 A non-quaternised polyester amide is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to sub-line addition pipe, nitrogen line and thermocouple/temperature controller system, 6 moles of 12-hydroxystearic acid and 1 mole of dimethylaminopropylamine where the reaction is carried out at about 130 °C and held for about 4 hours. The reaction mixture is then cooled to about 100 °C and zirconium butoxide is added, in an amount so that the catalyst makes up 0.57 percent by weight of the reaction mixture. The reaction mixture is heated to about 195 °C and held for about 12 hours. The resulting product is cooled and collected.
  • a quaternised polyester amide is prepared by placing 250g (lmol eq) of the product collected above in a 500mL flask with 64.68g dimethyl oxalate (4mol eq) and 1.48g octanoic acid (0.075mol eq). The reaction is heated with agitation under an atmosphere of nitrogen to 120 °C. Once at temperature, the reaction is held for 5 hours. After the hold, vacuum is applied to the vessel and the reaction is stripped of excess dimethyl oxalate at 120°C over a period of about 5 hours. After stripping, the quaternised polyester amide is cooled and collected without filtering.
  • Example 9 A non-quaternised polyester amide is prepared by reacting, in a jacketed reaction vessel fitted with stirrer, condenser, feed pump attached to sub-line addition pipe, nitrogen line and thermocouple/temperature controller system, 6 moles of ricinoleic acid and 1 mole of dimethylaminopropylamine where the reaction is carried out at about 130 °C and held for about 4 hours. The reaction mixture is then cooled to about 100 °C and zirconium butoxide is added, in an amount so that the catalyst makes up 0.57 percent by weight of the reaction mixture. The reaction mixture is heated to about 195 °C and held for about 12 hours. The resulting product is cooled and collected.
  • a quaternised polyester amide is prepared by placing 250g (lmol eq) of product collected above in a 500mL flask with 61.71g dimethyl oxalate (4mol eq) and 1.4 lg octanoic acid (0.075mol eq). The reaction is heated with agitation under an atmosphere of nitrogen to 120 °C. Once at temperature, the reaction is held for 5 hours. Vacuum is then applied and the reaction is stripped of excess dimethyl oxalate at 120°C over a period of about 5 hours. After stripping, the quaternised polyester amide is cooled and collected without filtering.
  • a series of engine lubricants are prepared containing the products of the examples above.
  • the engine lubricants include both heavy diesel (HD) and gasoline passenger car (PC) lubricants.
  • Engine Lubricant 1 is the same as CLE1 except it further contains 3 wt % of Example 4.
  • Engine Lubricant 3 is the same as CLE1 except it further contains 3 wt % of Example 5.
  • Engine Lubricant 4 is the same as CLE1 except it further contains 3 wt % of Example 7.
  • Engine Lubricant 5 is the same as CLE1 except it further contains 3 wt % of Example 2.
  • Lubricant Comparative Example 1 is a heavy duty diesel lubricant.
  • CLE2 is an API CJ-4 capable 15W-40 Lubricant containing 4.1 wt % of a succinimide dispersant.
  • the lubricant contains an 1.23 wt % of antioxidant system
  • Engine Lubricant 6 is the same as CLE2 except it further contains 3 wt % of Example 4.
  • Engine Lubricant 7 is the same as CLE2 except it further contains 3 wt % of Example 5.
  • Engine Lubricant 8 is the same as CLE2 except it further contains 3 wt % of Example 7.
  • Engine Lubricant 9 is the same as CLE2 except it further contains 3 wt % of Example 2.
  • the data indicates that adding a quaternised polyester salt of the present invention increases the panel coker rating. This means that the addition of quaternised polyester salt improves deposit cleanliness.
  • Engine Lubricant 10 is a passenger car gasoline engine lubricant.
  • EL10 is an API SM capable 5W-30 Lubricant containing 0 wt % of a succinimide dispersant, and 2 wt % of the product of Example 4.
  • the lubricant also contains 1.25 wt % of an antioxidant system (containing a mixture of aminic, phenolic and sulphur- containing antioxidants), 0.91 wt % of a zinc dialkyldithiophosphate, 0.62 wt % of an ethylene-propylene copolymer viscosity modifier, 0.14 wt % of pour point depressant, a 0.91 wt % of detergent system (containing a mixture of a sodium overbased sulphonate and calcium overbased sulphonate), 1 1 ppm of silioxane antifoam agent, and balance API Group II base oil.
  • an antioxidant system containing a mixture of aminic, phenolic and sulphur- containing antioxidants
  • 0.91 wt % of a zinc dialkyldithiophosphate 0.62 wt % of an ethylene-propylene copolymer viscosity modifier
  • Engine Lubricant 11 is a passenger car gasoline engine lubricant.
  • ELI 1 is an API SM capable 5W-30 Lubricant containing 1 wt % of a succinimide dispersant, and 1 wt % of the product of Example 4.
  • the lubricant also contains 1.25 wt % of an antioxidant system (containing a mixture of aminic, phenolic and sulphur- containing antioxidants), 0.91 wt % of a zinc dialkyldithiophosphate, 0.62 wt % of an ethylene-propylene copolymer viscosity modifier, 0.14 wt % of pour point depressant, a 0.91 wt % of detergent system (containing a mixture of a sodium overbased sulphonate and calcium overbased sulphonate), 1 1 ppm of silioxane antifoam agent, and balance API Group II base oil.
  • an antioxidant system containing a mixture of aminic, phenolic and sulphur- containing antioxidants
  • 0.91 wt % of a zinc dialkyldithiophosphate 0.62 wt % of an ethylene-propylene copolymer viscosity modifier
  • Engine Lubricant 12 is an API CJ-4 capable 15W-40 Lubricant containing 0 wt % of a succinimide dispersant, and 4.1 wt % of the product of Example 4.
  • the lubricant also contains 1.23 wt % of an antioxidant system (containing a mixture of aminic, phenolic and sulphur-containing antioxidants), 0.99 wt % of a zinc dialkyldithiophosphate, 1.24 wt % of an ethylene -propylene copolymer viscosity modifier, 0.08 wt % of pour point depressant, a 1.71 wt % of detergent system (containing a mixture of a sodium overbased sulphonate and calcium overbased sulphonate), 100 ppm of siloxane antifoam agent, 0.12 wt % of corrosion inhibitor, and balance API Group II base oil.
  • an antioxidant system containing a mixture of aminic, phenolic and sulphur-containing antioxidant
  • Engine Lubricant 13 is an API CJ-4 capable 15W-40 Lubricant containing 2.05 wt % of a succinimide dispersant, and 2.05 wt % of the product of Example 4.
  • the lubricant also contains 1.23 wt % of an antioxidant system (containing a mixture of aminic, phenolic and sulphur-containing antioxidants), 0.99 wt % of a zinc dialkyldithiophosphate, 1.24 wt % of an ethylene -propylene copolymer viscosity modifier, 0.08 wt % of pour point depressant, a 1.71 wt % of detergent system (containing a mixture of a sodium overbased sulphonate and calcium overbased sulphonate), 100 ppm of siloxane antifoam agent, 0.12 wt % of corrosion inhibitor, and balance API Group II base oil.
  • an antioxidant system containing a mixture of aminic, phenolic and sulphur-containing antioxidant
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.
  • hydrocarbyl substituents including aliphatic, alicyclic, and aromatic substituents
  • substituted hydrocarbon substituents that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent
  • hetero substituents that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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EP2723836B1 (de) 2018-08-08
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US20140107003A1 (en) 2014-04-17
WO2012177537A1 (en) 2012-12-27

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