EP2710102A1 - Compositions lubrifiantes pour turbines et systèmes hydrauliques à pouvoir antioxydant amélioré - Google Patents

Compositions lubrifiantes pour turbines et systèmes hydrauliques à pouvoir antioxydant amélioré

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Publication number
EP2710102A1
EP2710102A1 EP12724792.2A EP12724792A EP2710102A1 EP 2710102 A1 EP2710102 A1 EP 2710102A1 EP 12724792 A EP12724792 A EP 12724792A EP 2710102 A1 EP2710102 A1 EP 2710102A1
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EP
European Patent Office
Prior art keywords
component
percent
weight
composition
present
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.)
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Application number
EP12724792.2A
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German (de)
English (en)
Inventor
Seth L. Crawley
Betsy J. Butke
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
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Lubrizol Corp
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Publication date
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Publication of EP2710102A1 publication Critical patent/EP2710102A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2215/065—Phenyl-Naphthyl 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives 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
    • 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
    • C10M2223/043—Ammonium or amine 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2040/135—Steam engines or turbines

Definitions

  • the present invention relates to a synergistic combination of an antioxidant and an antiwear additive that results in improved antioxidancy performance in turbine, hydraulic, and other industrial lubricating compositions.
  • the invention further relates to the processes to make the improved lubricating compositions and methods of their use in industrial fluids.
  • This invention relates to compositions where aromatic amine antioxidants are used in combination with dithiocarbamates, in specific amounts, to synergistically improve the oxidative stability, and thus RBOT performance of industrial specialties lubricants in unexpected and surprising ways.
  • the invention provides for a composition that includes: (a) an oil of lubricating viscosity; (b) an aromatic amine antioxidant; and (c) a dithiocarbamate antiwear agent.
  • (b) is present from 0.35 to 0.75 percent by weight
  • component c) is present from 0.25 to 0.75 percent by weight
  • the total weight percent of the combination of components (b) and (c) is from 0.60 to 1.25 percent by weight, with regards to the overall composition.
  • the invention further allows for the addition of various other additives to the described compositions, in order to result in a fully formulated fluid.
  • compositions of the invention include an antioxidant other than component (b), an antiwear agent other than component (c), a corrosion inhibitor, a rust inhibitor, a foam inhibitor, a dispersant, a demulsifier, a metal deactivator, a friction modifier, a detergent, an emulsifier, an extreme pressure agent, or any combination thereof.
  • component (a) comprises a Group I base oil, a Group II base oil, a Group III base oil, or any combination thereof and is present from about 95 to about 99.9 percent by weight of the overall composition
  • component (b) comprises an alkylated diphenylamine and is present from about 0.35 to about 1.25, about 0.375 to about 0.75, or about 0.50 to about 0.75 percent by weight in the overall composition
  • component (c) comprises a dithiocarbamate ester and is present from about 0.25 to about 0.75 percent by weight in the overall composition
  • the total weight percent of the combination of components (b) and (c) is from 0.8 to 1.2 percent by weight, with regards to the overall composition
  • the composition further comprises: (d) an antioxidant other than component (b) that is present from about 0.01 to about 5.0 percent by weight of the overall composition; (e) an antiwear additive other than component (c) that is present from about 0.01 to about 2.5 percent by weight of the overall composition; (f) a corrosion
  • the invention further provides a process to prepare a lubricating oil composition comprising the steps of: (I) mixing together the components of the described compositions, in the described amounts. [0008] The invention further provides a method of lubricating a turbine system comprising the steps of: (I) supplying to a turbine system any of the compositions described herein.
  • the invention further provides a method of lubricating a hydraulic system comprising the steps of: (I) supplying to a turbine system any of the compositions described herein.
  • This invention concerns the synergistic combination of an aromatic amine antioxidant and a dithiocarbamate antiwear agent. Synergies are identified when a combination of two or more components provide a result that neither component on its own could have provided. The impact of treat rates must of course be taken into account as well, as the proper basis of comparison when identifying a synergy is very important. In addition, it is generally accepted that the performance benefit an additive imparts to a composition in which it is used increases with the treat rate. For example when you add an antioxidant to a lubricating composition, one would expect adding twice as much antioxidant would increase the benefit the additive provides to the composition.
  • a plot of performance against treat rate that levels off, or that shows a peak of improved performance and then drops off despite an increased treat rate for a particular combination of additives, where this improved performance is limited to particular treat rates and/or ratios, would by definition be a synergistic combination and a surprising result.
  • the invention provides for a composition that includes: (a) an oil of lubricating viscosity; (b) an aromatic amine antioxidant; and (c) a dithiocarbamate antiwear agent, where the amounts of (b) and (c) are present in amounts that provide a synergistic improvement in performance.
  • component (b) is present from 0.35 to 0.75 and may also be present from 0.375 to 0.7; 0.4 to 0.7; 0.4 to 0.6; 0.50 to 0.75, 0.5 to 0.7, 0.5 to 0.6 or even 0.5 percent by weight
  • component c) is present from 0.25 to 0.75 and may also be present from 0.3 to 0.75, 0.3 to 0.7, 0.4 to 0.6 or even 0.5 percent by weight
  • the total weight percent of the combination of components b) and c) is from 0.60 to 1.25 and may also be from 0.625 to 1.25, 0.75 to 1.25, 0.8 to 1.2, 0.9 to 1.1 or even 1.0 percent by weight, with regards to the overall composition.
  • the weight ratio of component b) to component c) is from 1 :0.5 to 1 : 1.5, or from 1 :0.5 to 1 :0.67, or from 1 : 1 to 1 : 1.67, or from 1 : 1 to 1 : 1.5, or from 1 :0.5 to 1 : 1. In some embodiments the weight ratio is 1 : 1. These weight ratios are in addition to ranges specified above for the combined treat rate of components b) and c), particularly where the combined treat rate of components b) and c) is from 0.60 to 1.25, 0.75 to 1.25, 0.75 to 1.0, 1.0 to 1.25, or even 1.0 percent by weight in the overall composition.
  • the invention also provides for methods of making and using the described compositions, in the lubrication of hydraulic systems and also in the lubrication of turbines.
  • One component of the compositions of the invention is an oil of lubricating viscosity, which can be present in a major amount, for a lubricant composition, or in a concentrate forming amount, for a concentrate.
  • Suitable oils include natural and synthetic lubricating oils and mixtures thereof.
  • the oil of lubricating viscosity is generally present in a major amount (i.e. an amount greater than 50 percent by weight).
  • the oil of lubricating viscosity is present in an amount of 75 to 95 percent by weight, and often greater than 80 percent by weight of the overall composition.
  • the base oil component generally makes up 100 parts by weight (pbw) of the overall
  • composition with the pbw ranges for the other components being provided with this 100 pbw of base oil in mind.
  • the pbw ranges of the various components, including the base oils are provided such that the total of the pbw of all components is 100.
  • the pbw ranges provided for the various components described below may be taken either way.
  • the lubricating oil component of the present invention is not overly limited, and may include a Group I, Group II or Group III base oil, or a combination thereof. These are classifications established by the API (American Petroleum Institute). Group III oils contain ⁇ 0.03 percent sulfur and > 90 percent saturates and have a viscosity index of > 120. Group II oils have a viscosity index of 80 to 120 and contain ⁇ 0.03 percent sulfur and > 90 percent saturates. The oil can also be derived from the hydroisomerization of wax, such as slack wax or a Fischer-Tropsch synthesized wax. Such "Gas-to-Liquid" oils are typically characterized as Group III base oils.
  • compositions of the present invention may also include Group IV and Group V base oils, either alone or in combination with any of the other oils discussed herein.
  • Polyalphaolefms are categorized as Group IV.
  • Group V encompasses "all others".
  • the lubricating oil component of the invention contains no more than 20, 10, 5, or even 1 percent by weight Group I base oil. These limits may also apply to Group IV or Group V base oils.
  • the lubricating oil present in the compositions of the invention is at least 60, 70, 80, 90, or even 95 percent by weight Group II and/or Group III base oil.
  • the lubricating oil present in the compositions of the invention is essentially only Group II and/or Group III base oil, where small amounts of other types of base oils may be present but not in amounts that significantly impact the properties or performance of the overall composition.
  • the lubricating oil component includes a Group I base oil, a Group II base oil, a Group III base oil, a poly(alpha-olefin), a GTL oil, or any combination thereof.
  • the base oil comprises a Group II base oil, a Group III base oil, a poly(alpha-olefm), a GTL oil, or any combination thereof.
  • the base oil comprises a Group II base oil.
  • the base oil component may be essentially or substantially free of Group I base oils.
  • the oil of lubricating viscosity may be present in the range from 60 to 99.9, from 95 to 99.9, 98.0 to 99.7, from 96.9 to 99.5, or from 98.5 to 99.4 weight percent of the lubricating oil composition.
  • Each oil of lubricating viscosity described above may be used alone or as mixtures of one or more thereof.
  • the invention provides for a composition that includes an aromatic amine antioxidant.
  • the antioxidant includes an alkylated diphenylamine and may be present from about 0.35 to about 0.75, or from 0.4 to about 0.7 percent by weight in the overall composition.
  • the aromatic amine antioxidant may also be present from 0.375 to 0.75, 0.5 to 0.75, 0.4 to 0.7, 0.35 to 0.65, 0.4 to 0.6, 0.45 to 0.55, 0.35 to 0.75, or from 0.375 to 0.7 or even 0.5 percent by weight in the overall composition.
  • Amines suitable for use in the invention may be represented by the formula:
  • R 1 and R 2 are independently a hydrogen or an alkyl group containing about 5 to 20 carbon atoms; or a linear or branched alkyl group containing 1 to 24 carbon atoms and q and r are each independently 0, 1 , 2, or 3, provided that the sum of q
  • R and R are independently hydrogen or alkyl groups containing 1 to 24, 4 to 20, 5 to 16, or 6 to 12 or even 10 carbon
  • each R and R may be a linear alkyl group, a branched alkyl group, or even an alkylaryl group.
  • alkylated diphenylamines of the invention are bis-nonylated diphenylamine and bis-octylated diphenylamine.
  • the invention provides for a composition that includes a dithiocarbamate antiwear agent.
  • the antiwear agent includes an ashless thiocarbamate, in some embodiments a thiocarbamate ester.
  • the thiocarbamates and ester thereof may be monothiocarbamates, dithiocarbamate, or mixtures thereof.
  • the antiwear agent is a dithiocarbamate ester and is present from about 0.25 or 0.3 to about 0.7 percent by weight in the overall composition.
  • the antiwear agent may be present from about 0.25, 0.3, 0.4 or even 0.5 up to 0.75, 0.7, 0.6 or even 0.55 percent by weight in the overall composition.
  • the antiwear agent is present from 0.25 to 0.75, 0.3 to 0.7, 0.35 to 0.65, 0.4 to 0.6, 0.45 to 0.55 or even 0.5 percent by weight in the overall composition.
  • the dithiocarbamate antiwear agent is represented by the formula:
  • R 3 and R 4 are independently alkyl of 1 to about 7 carbons, aryl, aralkyl or together form an alicyclic or heteroalicyclic radical in which the ring is completed through the nitrogen;
  • X is O or S;
  • a is 1 or 2;
  • R 5 and R 6 are independently H, alkyl or aryl; and
  • R is alkyl, aryl, aralkyl
  • -O-R -OH where R is alkylene of 1 to about 7 carbon atoms
  • -NR 10 R n where R 10 and R 11 are independently hydrogen, alkyl, cycloaliphatic, heteroalicyclic or together form an alicyclic or heteroalicyclic radical in which the ring is completed through the nitrogen
  • the compound is defined by the above formula where X is S, R 5 and R 6 are H or methyl, and Y is - OH, -OR 8° wherein R 8° is methyl or ethyl, -O-R 9 -OH, where R 9" is an alkylene of 1 to about 4 carbon atoms, or NR 10 R n wherein R 10 and R 11 are H.
  • compositions of the invention may also contain one or more additional additives.
  • the additional additives may include an antioxidant other than component b); an antiwear agent other than component c); a corrosion inhibitor, a rust inhibitor, a foam inhibitor, a dispersant, a demulsifier, a metal deactivator, a friction modifier, a detergent, an emulsifier, an extreme pressure agent, a pour point depressant, a viscosity modifier, or any combination thereof.
  • component (a) comprises a Group I base oil, a Group II base oil, a Group III base oil, or any combination thereof and is present from about 95 to about 99.9 percent by weight of the overall composition
  • component (b) comprises an alkylated diphenylamine and is present from about 0.4 to about 0.7 percent by weight in the overall composition
  • component (c) comprises a dithiocarbamate ester and is present from about 0.3 to about 0.7 percent by weight in the overall composition
  • the total weight percent of the combination of components (b) and (c) is from 0.8 to 1.2 percent by weight, with regards to the overall composition
  • the composition further comprises (d) an antioxidant other than component (b) that is present from about 0.01 to about 5.0 percent by weight of the overall composition
  • the composition further comprises (e) an antiwear additive other than component (c) that is present from about 0.01 to about 2.5 percent by weight of the overall composition
  • the composition further comprises (f) a corrosion inhibitor or metal deactivator that is present from about 0.001
  • component (a) may be present from 95 to 99.9, 98 to 99.7, or 98.5 to 99.5 percent by weight
  • component (b) may be present from 0.5 to 0.75, 0.4 to 0.7, 0.4 to 0.6, or even 0.5 percent by weight
  • component (c) may be present from 0.25 to 0.75, 0.3 to 0.7, 0.4 to 0.6, or even 0.5 percent by weight, where the combined treat rate of components (b) and (c) may be from 0.75 to 1.25, 0.8 to 1.2, 0.9 to 1.1, or even 1.0 percent by weight where all percent by weight values are in regards to the overall composition. In additional all of the weight ratios described above may be applied here as well.
  • component (d) may be present from 0.01 to 5.0, 0.01 to 1.5, 0.01 to 0.09 or even 0.09 percent by weight
  • component (e) may be present from 0.01 to 2.5, 0.01 to 1.5, 0.01 to 0.05 or even 0.05 percent by weight
  • component (f) may be present from 0.001 to 2.0, 0.001 to 1.0, 0.001 to 0.002, or even 0.002 percent by weight
  • component (g) may be present from 0.001 to 2.0, 0.001 to 1.0, 0.001 to 0.004, or even 0.004 percent by weight
  • component (h) may be present from 0.01 to 3.0, 0.01 to 1.5, 0.01 to 0.02, or even 0.02 percent by weight where all percent by weight values are in regards to the overall composition.
  • component (d) may include a sulfurized olefin, for example a substituted hydrocarbyl mono-sulfide, while component (e) may include an amine phosphate, component (f) may include a triazole, a tolyltriazole, or combinations thereof, component (g) may include a polyether, a fatty carboxylic acid or ester thereof, an ester of a nitrogen-containing carboxylic acid, an
  • component h) may include an acrylate copolymer. More specific examples of component (f) include hydrocarbyl substituted benzotriazole, 5-methylbenzotriazole, or a combination thereof.
  • component (d), the additional antioxidant includes a substituted hydrocarbyl mono-sulfide represented by the formula:
  • R 6 is a saturated or unsaturated branched or linear alkyl group with about 8 to about 20 carbon atoms; R 7 , R 8 , R 9 and R 10 are independently hydrogen or alkyl containing about 1 to about 3 carbon atoms.
  • the substituted hydrocarbyl monosulfides include n-dodecyl-2-hydroxyethyl sulfide, l-(tert- dodecylthio)-2-propanol, or combinations thereof.
  • the substituted hydrocarbyl monosulfide is l-(tert-dodecylthio)-2-propanol.
  • the additional antioxidant component may also include sterically hindered phenols represented by the formula:
  • R and R are independently branched or linear alkyl groups containing about 1 to about 24, preferably about 4 to about 18, and most preferably from about 4 to about 12 carbon atoms.
  • R and R may be either a straight or branched chain, branched is preferred.
  • the phenol is butyl substituted containing two t-butyl groups.
  • q is hydrogen or hydrocarbyl.
  • suitable hydrocarbyl groups include but are not limited to 2-ethylhexyl or n-butyl ester, dodecyl or mixtures thereof.
  • phenol is butyl substituted.
  • R 196 and R 20 are independently hydrogen, an arylalkyl group or a linear or branched alkyl group.
  • R 19 and R 20 are preferably in the para position.
  • the arylalkyl or alkyl groups contain about 1 to about 15, preferably about 1 to about 10, and most preferably about 1 to about 5 carbon atoms.
  • the bridging group Y includes but is not limited to -CH 2 - (methylene bridge) or -CH 2 OCH 2 - (ether bridge).
  • Examples of methylene -bridged sterically hindered phenols include but are not limited to 4,4 -methylenebis(6-tert-butyl o-cresol), 4,4 -methylenebis(2-tert- amyl-o-cresol), 2,2 -methylenebis(4-methyl-6-tert-butylphenol), 4,4 -methylene- bis(2,6-di-tertbutylphenol) or mixtures thereof.
  • the antioxidant is a hindered ester-substituted phenol represented by the formula:
  • compositions of the invention may also include dispersant additives. Suitable dispersants include: (i) polyetheramines; (ii) borated succinimide dispersants; (iii) non-borated succinimide dispersants; (iv) Mannich reaction products of a dialkylamine, an aldehyde and a hydrocarbyl substituted phenol; or any combination thereof. In some embodiments the dispersant component is present from 0.05 to 0.5 pbw of the overall composition.
  • Polyetheramines of the invention include compounds having two or more consecutive ether groups and at least one primary, secondary or tertiary amino group where the amine nitrogen has some basicity.
  • the polyetheramines of this invention include poly(oxyalkylene) amines having a sufficient number of repeating oxyalkylene units to render the poly(oxyalkylene)amine soluble in a base oil while allowing acceptable performance in ASTM D1401 (Standard Test Method for Water Separability of Petroleum Oils and Synthetic Fluids) test.
  • ASTM D1401 Standard Test Method for Water Separability of Petroleum Oils and Synthetic Fluids
  • poly(oxyalkylene)amines having at least about 5 oxyalkylene units are suitable for use in the present invention.
  • Poly(oxyalkylene)amines can include: hydrocarbylpoly(oxyalkylene)amines, hydrocarbylpoly(oxyalkylene)polyamines, and derivatives of polyhydric alcohols having at least two poly(oxyalkylene)amine and/or poly(oxyalkylene)polyamine chains on the molecule of the derivative.
  • the poly(oxyalkylene)amine for use in the invention is represented by the formula R-0-(AO) m -R 1 -N-R 2 R 3 wherein R is a hydrocarbyl group of 1 to 50 carbon atoms, or about 8 to about 30 carbon atoms; A is an alkylene group having 2 to 18 carbon atoms or 2 to 6 carbon atoms; m is a number from 1 to 50; R 1 is an
  • R and R are independently hydrogen, a hydrocarbyl group or -[R 4 N(R 5 )] n R 6 wherein R 4 is an alkylene group having 2 to 6 carbon atoms, R 5 and R 6 are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.
  • poly(oxyalkylene)amine of the present invention can be represented by the formula:
  • the poly(oxyalkylene)amine of the present invention can be represented by the formula: CH 3 CH(CH 3 )[CH 2 CH(CH 3 )] 2 CH(CH 3 )CH 2 CH 2 0- [CH 2 CH(CH 2 CH 3 )0] m CH 2 CH 2 CH 2 NH 2 wherein m is a number from about 16 to about 28.
  • Poly(oxyalkylene)amines of the present invention can have a molecular weight in the range from about 300 to about 5,000.
  • the polyetheramines of the present invention can be prepared by initially condensing an alcohol or alkylphenol with an alkylene oxide, mixture of alkylene oxides or with several alkylene oxides in sequential fashion in a 1 : 1-50 mole ratio of hydric compound to alkylene oxide to form a polyether intermediate.
  • U.S. Patent Nos. 5,112,364 and 5,264,006 provide reaction conditions for preparing a polyether intermediate.
  • the alcohols can be monohydric or polyhydric, linear or branched, saturated or unsaturated and having 1 to 50 carbon atoms, or from 8 to 30 carbon atoms, or from 10 to 16 carbon atoms.
  • Branched alcohols of the present invention can include Guerbet alcohols, as described in U.S. Patent No. 5,264,006, which generally contain between 12 and 40 carbon atoms and can be represented by the formula R-CH(CH 2 CH 2 R)CH 2 0H where R is a hydrocarbyl group.
  • the alkyl group of the alkylphenols can be 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10 to 20 carbon atoms.
  • the alkylene oxides include 1 ,2-epoxyalkanes having 2 to 18 carbon atoms, or 2 to 6 carbon atoms.
  • the alkylene oxides can be ethylene oxide, propylene oxide and butylene oxide. Especially useful is propylene oxide, butylene oxide, or a mixture thereof.
  • the number of alkylene oxide derived units in the polyether intermediate can be 1-50, or 12-30, or 16-28.
  • the polyether intermediates can be converted to polyetheramines by several methods.
  • the polyether intermediate can be converted to a polyetheramine by a reductive amination with ammonia, a primary amine or a polyamine as described in U.S. Patent Nos. 5,112,364 and 5,752,991.
  • the polyether intermediate can be converted to a polyetheramine via an addition reaction of the polyether to acrylonitrile to form a nitrile which is then hydrogenated to form the polyetheramine.
  • U.S. Patent No. 5,264,006 provides reaction conditions for the cyanoethylation of the polyether with acrylonitrile and the subsequent hydrogenation to form the polyetheramine.
  • the polyether intermediate or poly(oxyalkylene) alcohol is converted to the corresponding poly(oxyalkylene) chloride via a suitable chlorinating agent followed by displacement of chlorine with ammonia, a primary or secondary amine, or a polyamine as described in U.S. Patent No. 4,247,301.
  • the polyetheramine of the present invention is derived from the reaction of a mixture of alcohols containing from 10 to 18 carbon atoms, an alkoxylate and an amine.
  • Succinimide dispersants are well known in the field of lubricants and include primarily what are sometimes referred to as “ashless" dispersants because they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant.
  • Succinimide dispersants are the reaction product of a hydrocarbyl substituted succinic acylating agent and an amine containing at least one hydrogen attached to a nitrogen atom.
  • succinic acylating agent refers to a hydrocarbon-substituted succinic acid or succinic acid- producing compound (which term also encompasses the acid itself). Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
  • Succinic based dispersants have a wide variety of chemical structures including typically structures such as:
  • each R Z4 is independently a hydrocarbyl group, which may be bound to multiple succinimide groups, typically a polyolefm-derived group having a number average molecular weight (Mn) of 500 or 700 to 10,000.
  • the hydrocarbyl group is an alkyl group, frequently a polyisobutylene group derived from polyisobutylene with a Mn of 500 or 700 to 5000, or 1500 or
  • the R groups can contain 40 to 500 carbon atoms or at least 50 to 300 carbon atoms, e.g., aliphatic carbon atoms.
  • the R are alkylene groups, commonly ethylene (C 2 H 4 ) groups. Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts. Succinimide dispersants are more fully described in U.S. Patents 4,234,435, 3,172,892, and 6,165,235.
  • the polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms.
  • Each R 1 group may contain one or more reactive groups, i.e. succinic groups.
  • the amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines. In either case they will be characterized by the formula R 4 R 5 NH wherein R 4 and R 5 are each independently hydrogen, hydrocarbon, amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, or acylimidoyl groups provided that no more than one of R 4 and R 5 is hydrogen. In all cases, therefore, they will be characterized by the presence within their structure of at least one H-N ⁇ group.
  • H 2 N- primary
  • secondary amino i.e., H-N ⁇
  • monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, and octadecylamine.
  • the polyamines from which the dispersant is derived include principally alkylene amines conforming, for the most part, to the formula
  • A is hydrogen or a hydrocarbyl group typically having up to 30 carbon atoms
  • the alkylene group is typically an alkylene group having less than 8 carbon atoms.
  • the alkylene amines include principally, ethylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines.
  • ethylene diamine diethylene triamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(-trimethylene) triamine.
  • Higher homologues such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful. Tetraethylene pentamine is particularly useful.
  • ethylene amines also referred to as polyethylene polyamines
  • polyethylene polyamines are especially useful. They are described in some detail under the heading "Ethylene Amines” in Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).
  • Hydroxyalkyl-substituted alkylene amines i.e., alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are useful.
  • examples of such amines include N-(2-hydroxyethyl)ethylenediamine, N,N ' -bis(2- hydroxyethyl)-ethylenediamine, 1 -(2-hydroxyethyl)piperazine, monohydroxy- propyl)-piperazine, di-hydroxypropyl-substituted tetraethylenepentamine, N-(3- hydroxypropyl)-tetra-methylenediamine, and 2-heptadecyl-l -(2-hydroxyethyl)- imidazoline.
  • the succinimide dispersant is referred to as such since it normally contains nitrogen largely in the form of imide functionality, although it may be in the form of amine salts, amides, imidazolines as well as mixtures thereof.
  • To prepare the succinimide dispersant one or more of the succinic acid-producing compounds and one or more of the amines are heated, typically with removal of water, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent at an elevated temperature, generally in the range of 80°C up to the decomposition point of the mixture or the product; typically 100°C to 300°C.
  • the succinic acylating agent and the amine are typically reacted in amounts sufficient to provide at least one-half equivalent, per equivalent of acid-producing compound, of the amine (or hydroxy compound, as the case may be).
  • the maximum amount of amine present will be about 2 moles of amine per equivalent of succinic acylating agent.
  • an equivalent of the amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogen atoms present.
  • the number of equivalents of succinic acid- producing compound will vary with the number of succinic groups present therein, and generally, there are two equivalents of acylating reagent for each succinic group in the acylating reagents. Additional details and examples of the procedures for preparing the succinimide detergents of the present invention are included in, for example, U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 4,234,435; 6,440,905 and 6,165,235.
  • compositions of the invention include a non- borated succinimide dispersant derived from polyisobutylene having a number average molecular weight from 500 to 3000 and polyethylenepolyamines.
  • the succinimide dispersants above may be borated.
  • Borated dispersants are well-known materials and can be prepared by treating one or more of dispersants described above with a borating agent such as boric acid. Typical conditions include heating the dispersant with boric acid at 100 to 150 degrees C.
  • the dispersants may also be treated by reaction with maleic anhydride as described in PCT application US99/23940 filed 13 Oct. 1999.
  • compositions of the invention include a borated succinimide dispersant derived from polyisobutylene having a number average molecular weight from 500 to 3000 and polyethylenepolyamines.
  • the composition contains less than 0.1 pbw of fatty carboxylic acids.
  • the dispersant of the invention can be a Mannich dispersant.
  • Mannich dispersants are the reaction product of a hydrocarbyl-substituted phenol, an aldehyde, and an amine or ammonia, but in this invention generally a dialkylamine.
  • the hydrocarbyl substituent of the hydrocarbyl-substituted phenol can have 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms, and in a further instance 10 or 40 to 110 carbon atoms.
  • This hydrocarbyl substituent can be derived from an olefin or a polyolefm.
  • Useful olefins include alpha-olefms, such as 1- decene, which are commercially available.
  • the polyolefms which can form the hydrocarbyl substituent can be prepared by polymerizing olefin monomers by well known polymerization methods and are also commercially available.
  • the olefin monomers include monoolefms, including monoolefms having 2 to 10 carbon atoms such as ethylene, propylene, 1- butene, isobutylene, and 1 -decene.
  • An especially useful monoolefm source is a C 4 refinery stream having a 35 to 75 weight percent butene content and a 30 to 60 weight percent isobutene content.
  • Useful olefin monomers also include diolefms such as isoprene and 1,3 -butadiene.
  • Olefin monomers can also include mixtures of two or more monoolefms, of two or more diolefms, or of one or more monoolefms and one or more diolefms.
  • Useful polyolefms include polyisobutylenes having a number average molecular weight of 140 to 5000, in another instance of 400 to 2500, and in a further instance of 140 or 500 to 1500.
  • the polyisobutylene can have a vinylidene double bond content of 5 to 69 percent, in a second instance of 50 to 69 percent, and in a third instance of 50 to 95 percent.
  • the polyolefm can be a homopolymer prepared from a single olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. Also possible as the hydrocarbyl substituent source are mixtures of two or more homopolymers, two or more copolymers, or one or more homopolymers and one or more copolymers.
  • the hydrocarbyl-substituted phenol can be prepared by alkylating phenol with an olefin or polyolefm described above, such as a polyisobutylene or polypropylene, using well-known alkylation methods.
  • the aldehyde used to form the Mannich dispersant can have 1 to 10 carbon atoms, and is generally formaldehyde or a reactive equivalent thereof such as formalin or paraformaldehyde.
  • the amine used to form the Mannich dispersant can be a monoamine or a polyamine, including alkanolamines having one or more hydroxyl groups.
  • Useful amines include ethanolamine, diethanolamine, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2-(2-amino- ethylamino) ethanol.
  • the Mannich dispersant can be prepared by reacting a hydrocarbyl-substituted phenol, an aldehyde, and an amine as described in U.S. Patent No. 5,697,988.
  • the Mannich reaction product is prepared from an alkylphenol derived from a polyisobutylene, formaldehyde, and an amine that is a primary monoamine, a secondary monoamine, or an alkylenediamine, in particular, ethylenediamine or dimethylamine.
  • the Mannich is prepared from a dialkylamine or a dialkenylamine.
  • the Mannich reaction product of the present invention can be prepared by reacting the alkyl-substituted hydroxyaromatic compound, aldehyde and polyamine by well known methods including the method described in U.S. Patent 5,876,468.
  • the Mannich reaction product can be prepared by well known methods generally involving reacting the hydrocarbyl substituted hydroxy aromatic compound, an aldehyde and an amine at temperatures between 50 to 200°C in the presence of a solvent or diluent while removing reaction water as described in U. S. Patent No. 5,876,468.
  • compositions of the present invention contain a Mannich reaction product derived from the reaction of a dialkylamine, formaldehyde, and a polyisobutylene substituted phenol where the polyisobutylene has a number average molecular weight from 500 to 3000.
  • the Mannich dispersant may be present in the overall composition from 0.07 to 0.44 pbw, from 0.05, 0.07, or even 0.088 up to 0.5, 0.45, or even 0.44 pbw.
  • compositions may include still other additives, including: a foam inhibitor, a demulsifier, a pour point depressant, or mixtures thereof.
  • the optional additives may be present in the range from 0.0005 to 1.3, from 0.00075 to 0.5, from 0.001 to 0.4, or from 0.0015 to 0.3 percent by weight of the composition, where these ranges may be applied to the total of all of these additional additives, or to each one individually.
  • Antifoams also known as foam inhibitors, are known in the art and include but are not limited to organic silicones and non- silicon foam inhibitors. Examples of organic silicones include dimethyl silicone and polysiloxanes.
  • non-silicon foam inhibitors include but are not limited to copolymers of ethyl acrylate and 2-ethylhexylacrylate, copolymers of ethyl acrylate, 2- ethylhexylacrylate and vinyl acetate, polyethers, polyacrylates and mixtures thereof.
  • the antifoam is a polyacrylate. Antifoams may be present in the composition from 0.001 to 0.012 or 0.004 pbw or even 0.001 to 0.003.
  • Demulsifiers are known in the art and include but are not limited to derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or polyamines reacted sequentially with ethylene oxide or substituted ethylene oxides or mixtures thereof.
  • demulsifiers include polyethylene glycols, polyethylene oxides, polypropylene oxides, (ethylene oxide -propylene oxide) polymers and mixtures thereof.
  • the demulsifiers is a polyether. Demulsifiers may be present in the composition from 0.002 to 0.012 pbw.
  • Pour point depressants are known in the art and include but are not limited to esters of maleic anhydride-styrene copolymers, polymethacrylates;
  • polyacrylates polyacrylamides; condensation products of haloparaffm waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkyl phenol formaldehyde condensation resins, alkyl vinyl ethers and mixtures thereof.
  • compositions of the invention may also include a rust inhibitor.
  • Suitable rust inhibitors include hydrocarbyl amine salts of alkylphosphoric acid, hydrocarbyl amine salts of dialkyldithiophosphoric acid, hydrocarbyl amine salts of hydrocarbyl aryl sulphonic acid, fatty carboxylic acids or esters thereof, an ester of a nitrogen-containing carboxylic acid, an ammonium sulfonate, an imidazoline, or any combination thereof; or mixtures thereof.
  • Suitable hydrocarbyl amine salts of alkylphosphoric acid of the invention are represented by the following formula:
  • R and R are independently hydrogen, alkyl chains or hydrocarbyl
  • R and R z ' are hydrocarbyl.
  • R and R contain about 4 to about 30, preferably about 8 to about 25, more preferably about 10 to about 20,
  • R , R and R are independently hydrogen, alkyl branched or linear alkyl chains with about 1 to about 30, preferably about 4 to about 24, even more preferably about 6 to about 20, and
  • R , R and R are independently hydrogen, alkyl branched or linear alkyl chains, preferably at least
  • R , R and R are hydrogen.
  • alkyl groups suitable for R , R and R include but are not limited to butyl, sec butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec hexyl, n-octyl, 2- ethyl, hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures thereof.
  • the hydrocarbyl amine salt of an alkylphosphoric acid is the reaction product of a C14 to Ci 8 alkylated phosphoric acid with Primene 81R (produced and sold by Rohm & Haas) which is a mixture of Cn to Ci 4 tertiary alkyl primary amines.
  • Hydrocarbyl amine salts of dialkyldithiophosphoric acid of the invention used in the rust inhibitor package are represented by the formula:
  • R 31 and R 32 are independently branched or linear alkyl groups.
  • R 31 and R 32 contain about 3 to about 30, preferably about 4 to about 25, more preferably about
  • hydrocarbyl amine salts of dialkyldithiophosphoric acid of the invention include but are not limited to the reaction product(s) of heptyl or octyl or nonyl dithiophosphoric acids with ethylene diamine, morpholine or Primene 81R or mixtures thereof.
  • Suitable hydrocarbyl amine salts of hydrocarbyl aryl sulphonic acids used in the rust inhibitor package of the invention are represented by the formula:
  • R is a hydrocarbyl group with about 4 to about 30, preferably about 6 to about 25, more preferably about 8 to about 20 carbon atoms, z is independently 1, 2, 3, or 4 and most preferably z is 1 or 2.
  • R 28 is a hydrocarbyl group with about 4 to about 30, preferably about 6 to about 25, more preferably about 8 to about 20 carbon atoms, z is independently 1, 2, 3, or 4 and most preferably z is 1 or 2.
  • R JU are as described above.
  • hydrocarbyl amine salts of hydrocarbyl aryl sulphonic acid of the invention include but are not limited to the ethylene diamine salt of dinonyl naphthalene sulphonic acid.
  • Suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid.
  • An example of a suitable ester of a nitrogen- containing carboxylic acid includes oleyl sarcosine.
  • the rust inhibitors may be present in the range from 0.02-0.2, from 0.03 to 0.15, from 0.04 to 0.12, or from 0.05 to 0.1 pbw of the lubricating oil composition.
  • the rust inhibitors of the invention may be used alone or in mixtures thereof.
  • the lubricating compositions of the invention may also include a metal deactivator.
  • Metal deactivators are used to neutralise the catalytic effect of metal for promoting oxidation in lubricating oil. Suitable metal deactivators include but are not limited to triazoles, tolyltriazoles, a thiadiazole, or combinations thereof, as well as derivatives thereof. Examples include derivatives of benzotriazoles,
  • benzimidazole 2-alkyldithiobenzimidazoles, 2-alkyldithiobenzothiazoles, 2-(N,N'- dialkyldithio-carbamoyl)benzothiazoles, 2,5-bis(alkyl-dithio)-l,3,4-thiadiazoles, 2,5-bis(N,N'-dialkyldithiocarbamoyl)-l,3,4-thiadiazoles, 2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof.
  • the metal deactivator is a hydrocarbyl substituted benzotriazole compound.
  • the benzotriazole compounds with hydrocarbyl substitutions include at least one of the following ring positions 1- or 2- or 4- or 5- or 6- or 7- benzotriazoles.
  • the hydrocarbyl groups contain about 1 to about 30, preferably about 1 to about 15, more preferably about 1 to about 7 carbon atoms, and most preferably the metal deactivator is 5-methylbenzotriazole used alone or mixtures thereof.
  • the metal deactivators may be present in the range from 0.001 to 0.1, from 0.01 to 0.04 or from 0.015 to 0.03 pbw of the lubricating oil composition. Metal deactivators may also be present in the composition from 0.002 or 0.004 to 0.02 pbw. The metal deactivator may be used alone or mixtures thereof.
  • compositions of the invention are useful as hydraulic, turbine and other industrial application lubricating compositions.
  • the additives described may also be in the form of an additive concentrate that can then be diluted with base oil to produce a final lubricating composition.
  • the relative proportions of the various additives would remain the same.
  • the percent by weight values provided above may be applied as pbw values for an additive concentrate, except for the base oil component.
  • the concentrate would contain small amount of base oil, or some other diluent, and in some embodiments no base oil or diluent at all.
  • the concentrates would contain sufficient base oil and/or diluent to ensure they have good handling properties.
  • the description of process below regarding the preparation of various lubricating compositions may also be red in terms of additive concentrate applications.
  • the invention further provides a process for preparing a composition
  • a process for preparing a composition comprising the steps of: (I) mixing together: a) an oil of lubricating viscosity; b) an aromatic amine antioxidant; and c) a dithiocarbamate antiwear agent.
  • the compositions may optionally include one or more additional additives.
  • Component b) may be present from 0.35, 0.375 or even 0.5 to 0.75 percent by weight, component c) may be present from 0.25 to 0.75 percent by weight, and the total weight percent of the combination of components b) and c) may be from 0.60, 0.625 or even 0.75 to 1.25 percent by weight, with regards to the overall composition.
  • all of the ranges and examples of the various components provided above may apply here to the described processes as well.
  • the invention also provides methods of lubricating a turbine system, a hydraulic system, of any combination thereof, where the process includes the steps: I. supplying to the system a lubricating composition comprising: a) an oil of lubricating viscosity; b) an aromatic amine antioxidant; and c) a dithiocarbamate antiwear agent.
  • a lubricating composition comprising: a) an oil of lubricating viscosity; b) an aromatic amine antioxidant; and c) a dithiocarbamate antiwear agent.
  • the compositions may optionally include one or more additional additives.
  • Component b) may be present from 0.35, 0.375 or even 0.5 to 0.75 percent by weight, component c) may be present from 0.25 to 0.75 percent by weight, and the total weight percent of the combination of components b) and c) may be from 0.60, 0.625 or even 0.75 to 1.25 percent by weight, with regards to the overall composition.
  • all of the ranges and examples of the various components provided above may apply here to the described processes as well.
  • substituted thiadiazoles which contain an aromatic ring in their structure can in some cases have a negative impact on the oxidation properties of the compositions in which they are used. Thus poorer oxidation properties in compositions containing such materials is expected, independent of the benefits of the invention. Still, in some embodiments the invention limits the presence of such materials. In some embodiments substituted thiadiazoles which contain an aromatic ring as a substituent group are present at less than 0.25 percent by weight in the overall composition, at less than 0.20 or 0.15 percent by weight. In some embodiments the compositions of the invention contains no more than 0.10 percent by weight substituted thiadiazoles which contain an aromatic ring as a substituent group. In still other embodiments the compositions of the invention are essentially, substantially, or even completely free of such materials.
  • alkylated phenols are present at less than 0.25 percent by weight in the overall composition, at less than 0.20 or 0.15 percent by weight. In some embodiments the compositions of the invention contains no more than 0.10 percent by weight alkylated phenols. In still other embodiments the compositions of the invention are essentially, substantially, or even completely free of such materials.
  • a portion of oil or similar diluent is present with the components and the components are mixed into the oil.
  • a minimal amount of oil or diluent is present, other than that amount inherently present in the additive from their means of production and preparation and additional base oil is added after the component have been mixed. In any event the described processes results in lubricating compositions.
  • the lubricating oil compositions may be prepared from a concentrate comprising the steps of: a) mixing all of the components described above with minimal oil and/or diluent present, other than optionally some relatively small amount to allow for reasonable handling properties.
  • the resulting concentrate may then be used in the preparation of a lubricating composition by mixing the concentrate with an effective amount of base oil or mixtures thereof resulting in a finished fluid.
  • Optional additives may be added to the concentrate or to the resulting final fluid. These optional additives include any of those described above.
  • these optional additives include a foam inhibitor, a demulsifier, a viscosity modifier, a pour point depressant, or mixtures thereof, and may be added such that they are present in the overall compositions in the range about 0, 0.01, 0.1 or even 0.25 or up to about 13, 10, 8 or even 6 pbw.
  • compositions of the present invention may be used as industrial fluids, hydraulic fluids, turbine oils and circulating oils and combinations thereof.
  • the compositions are used in steam and gas turbine systems.
  • the use of the lubricating oil composition in such systems may improve the oxidative and/or thermal stability of the formulation.
  • the invention further provides a method of lubricating a steam or gas turbine comprising the steps of supplying to said turbine any of the lubricating compositions described herein.
  • compositions are prepared and tested to evaluate their oxidative and thermal stability, as measured by the Rotary Bomb Oxidation Test (RBOT), which is based on ASTM D2272.
  • RBOT Rotary Bomb Oxidation Test
  • a samples oxidation life is measured.
  • the samples are reacted with oxygen, water and a copper catalyst coil at 150 degrees C in a rotating bomb unit.
  • the bomb is sealed and the pressure in the unit is measured over time. Decreasing pressure indicates the extent and rate of oxidative reactions taking place in the sample.
  • the time it takes for the pressure in the unit to drop 172.4 kPascals (2.5 psi) from the maximum pressure is recorded for each sample.
  • the longer the time it takes for the pressure to drop the specified amount the more resistant the sample is to oxidation and the more stable the sample is.
  • a set of six samples is prepared for this testing. Each sample has the exact same formulation except for the amounts of the aromatic amine antioxidant (AO) and the dithiocarbamate antiwear agents (AW). Each sample contains the same amount of an identical additive package that contains mixtures of phosphoric acid esters and amine salts, a sulfurized olefin secondary antioxidant, an acrylate polymer antifoam agent, a triazole metal deactivator, a polyether copolymer corrosion inhibitor, and lubricating oil. All of these examples were prepared in the same Group II base oil. The table below summarizes the formulation of the sample set and the RBOT results each sample provided:
  • the data also shows a significantly improved peak of performance when the amount of component (b) present is more than 0.375% and less than 0.75% by weight, and the amount of component (c) present is more than 0.25% and less than 1.25% by weight, and the total combined amount of components (b) and (c) is from 0.625%) up to 1.25% by weight.
  • the data also shows that the high performing examples have a ratio for (b) to (c) from 1 : 1.33 to 1 :0.67.
  • Example 3 shows this combination gives the best results, particularly at a 1 : 1 ratio, better than any of the other samples, including samples at higher and lower treat rates and weight ratios.
  • Example Set 2 A second example set of compositions is prepared and tested to evaluate their oxidative and thermal stability, again using the RBOT test described above.
  • the formulations of these examples, particularly the additional additives present vary widely.
  • the formulations of these examples and the results obtained are summarized in the tables below. It is noted that the relative amounts of the individual additives listed in each additive package may vary slightly from example to example, but all of the additives listed in a given additive package are present in each example indicated and in comparable amounts.
  • Example 2 The base oil component makes up the balance of each composition.
  • Example 2-1 uses the same group II base oil used in Example Set 1, while Examples 2-2 to 2-8 use a mixture of a 650N Group II base oil and a Group II base oil from Petro-Canada.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package A is a combination of conventional additives, and includes a sulfurized olefin secondary antioxidant, a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts, and diluent oil.
  • Additive Package B is a combination of convention additives and includes a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts, and diluent oil.
  • Additive Package C is a combination of conventional additives, and includes mixtures of phosphoric acid esters and amine salts, a sulfurized olefin secondary antioxidant, an acrylate polymer antifoam agent, a triazole metal deactivator, a polyether copolymer corrosion inhibitor, and diluent oil.
  • Additive Package D is a combination of conventional additives, and includes a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts, and diluent oil.
  • Examples 2-9 to 2-16 use the same base oil mixture used in Examples 2-2 to 2-8, described above.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package E is a combination of conventional additives, and includes a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts, a substituted thiadiazole that does not contain an aromatic ring in its structure, and diluent oil.
  • Additive Package F is the same as Additive Package E except there are no substituted thiadiazole that does not contain an aromatic ring in its structure present in the additive package.
  • Additive Package G is the same as Additive Package E except there are no substituted thiadiazole that does not contain an aromatic ring in its structure present in the additive package and the additive package further includes a phosphite antiwear agent.
  • Examples 2-17 to 2-24 use the same base oil mixture used in Examples 2-2 to 2-8, described above.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package F is the same as that described in footnote 6 of Table 2b above.
  • Additive Package G is the same as that described in footnote 7 of Table 2b above.
  • 8 - Additive Package H is the same as Additive Package G except it further contains a substituted thiadiazole that does not contain an aromatic ring in its structure.
  • Additive Package I is the same as Additive Package F except it further contains a substituted thiadiazole that does not contain an aromatic ring in its structure.
  • Examples 2-25 to 2-30 use the same base oil mixture used in Examples 2-2 to 2-8, described above.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package J is the same as Additive Package I except that the package does not contain a substituted thiadiazole , and the package further contains a alkenyl phosphite antiwear additive.
  • Additive Package K is the same as Additive Package K except it further contains a substituted thiadiazole that does not contain an aromatic ring in its structure.
  • a third example set of compositions is prepared and tested to evaluate their oxidative and thermal stability, again using the RBOT test described above.
  • the formulations of these examples, particularly the additional additives present vary widely.
  • the formulations of these examples and the results obtained are summarized in the tables below. It is noted that the relative amounts of the individual additives listed in each additive package may vary slightly from example to example, but all of the additives listed in a given additive package are present in each example indicated and in comparable amounts.
  • Example 3-1 to 3-8 all use the same base oil, a mixture of a 530N Group II base oil and a Group II base oil from Petro-Canada.
  • 3 - Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package L is a combination of conventional additives including a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts, a fatty acid friction modifier, and diluent oil.
  • Additive Package M is the same as Additive Package L except it does not include a fatty acid friction modifier, while it further includes a substituted thiadiazole that does not contain an aromatic ring in its structure and an amine-containing friction modifier.
  • Additive Package N is the same as Additive Package L except it does not include the polyether corrosion inhibitor or fatty acid friction modifier, but it further includes another polyether additive.
  • Additive Package O is the same as Additive Package M except that it does not include amine- containing friction modifier, while it does include a fatty acid friction modifier.
  • Example 3-1 to 3-8 all use the same base oil, a mixture of a 530N Group II base oil and a Group II base oil from Petro-Canada.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • a fourth example set of compositions is prepared and tested to evaluate their oxidative and thermal stability, again using the RBOT test described above.
  • the formulations of these examples, particularly the additional additives present vary widely.
  • the formulations of these examples and the results obtained are summarized in the tables below. It is noted that the relative amounts of the individual additives listed in each additive package may vary slightly from example to example, but all of the additives listed in a given additive package are present in each example indicated and in comparable amounts.
  • the base oil component makes up the balance of each composition.
  • Examples 4-1 to 4-8 all use the same base oil, a mixture of two Group II base oils, different from those used above.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples.
  • An alkylated phenol is present in some compositions as a secondary antioxidant.
  • Additive Package P is the same as Additive Package B except it does not include the polyether corrosion inhibitor, while it further includes a different polyether additive.
  • Additive Package Q is the same as Additive Package B it further includes an amine containing friction modifier.
  • Additive Package R is the same as Additive Package P except it does not include the mixtures of phosphoric and/or dithiophosphoric acid esters and amine salts.
  • the base oil component makes up the balance of each composition.
  • Examples 4-11 to 4-14 all use the same base oil, a mixture of two Group II base oils, different from those used above.
  • Examples 4-15 and 4-16 uses a different mixture of two different Group II base oils.
  • Example 4-9 uses still another mixture of Group II base oils and
  • Example 4-10 includes on of these base oils combined with yet another Group II base oil. All of the base oils used in these examples are commercially available Group II base oils.
  • Corrosion Inhibitor I is a substituted thiadiazole that contains an aromatic ring in its structure as a substituent group. It is the only corrosion inhibitor with such a group present in these examples. 4 - An alkylated phenol is present in some compositions as a secondary antioxidant. The alkylated phenol in the examples in this table has a different alkyl group than that used in the examples above.
  • Additive Package S is a combination of conventional additives including a polyether corrosion inhibitor, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, a salicylic acid based detergent, and diluent oil.
  • Additive Package T is the same as Additive Package R, described in footnote 8 of Table 4a above, except that it further includes a polyether amine.
  • Additive Package U is the same as Additive Package T, except that it further includes a salicylic acid based detergent.
  • 9 - Additive Package V is a combination of conventional additives including an antiwear additive containing a mixture of phosphoric acid ester and/or amine salts thereof, an ester copolymer antifoam agent, a substituted triazole corrosion inhibitor, a polyether additive, and an alkyl benzene.
  • Additive Package V Wis the same as Additive Package V except that it does not include the mixture of phosphoric acid ester and/or amine salts thereof.
  • hydrocarbyl substituent or “hydrocarbyl group,” as used herein are used in their ordinary sense, which is well-known to those skilled in the art. Specifically, they refer to a group primarily composed of carbon and hydrogen atoms that is attached to the remainder of the molecule through a carbon atom and does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the molecule having a predominantly hydrocarbon character. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group. A more detailed definition of the terms "hydrocarbyl substituent” or “hydrocarbyl group,” is described in US Patent 6, 583,092.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une combinaison synergique associant un antioxydant et un additif anti-usure, avec pour résultat des performances antioxydantes améliorées pour les compositions lubrifiantes pour turbine et systèmes hydrauliques et les autres compositions lubrifiantes industrielles en contenant. L'invention concerne, en outre, les procédés de fabrication de ces compositions lubrifiantes améliorées et leurs procédés d'utilisation dans des liquides industriels.
EP12724792.2A 2011-05-16 2012-05-14 Compositions lubrifiantes pour turbines et systèmes hydrauliques à pouvoir antioxydant amélioré Withdrawn EP2710102A1 (fr)

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CA2834078A1 (fr) 2012-11-22
JP2014515058A (ja) 2014-06-26

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