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
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2219/068—Thiocarbamate metal 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/12—Groups 6 or 16
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

• This invention relates to lubricating oil compositions, more especially to compositions suitable for use in piston engine, especially gasoline (spark-ignited) and diesel (compression-ignited), crankcase lubrication.
• Such compositions may be referred to as crankcase lubricants.
• ZDDP's zinc dialkyldithiophosphates
• a problem arising from the use of ZDDP's is their phosphorus content: phosphorus derivatives deriving from the ZDDP's can poison the components of exhaust gas catalytic converters.
• Catalytic converters are used to reduce pollution and to meet governmental regulations requiring reduction in the levels of undesirable gases, such as hydrocarbons, carbon monoxide, and oxides of nitrogen, from internal engine combustion exhaust emissions.
• Such converters use catalysts which are installed in the exhaust streams, e.g. the exhausts of automobiles, to treat the undesirable gases.
• Phosphorus derivatives, such as decomposition products of ZDDP's can be carried into the exhaust, where they are believed to poison the catalyst.
• engine oils containing phosphorus additives may substantially reduce the life and effectiveness of catalytic converters. Therefore, it would be desirable to reduce, or eliminate, the phosphorus-content of engine oils so as to maintain the activity and extend the life of catalytic converters. Also, it is possible that sulfur-containing components may poison the catalysts, for example those used to reduce the levels of oxides of nitrogen.
• the invention provides a crankcase lubricating oil composition
• a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 200 ppm by mass of boron, less than 600 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition.
• the invention provides a crankcase lubricating oil composition
• a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 300 ppm by mass of boron, less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition.
• the invention provides a crankcase lubricating oil composition
• a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive, a detergent additive composition and one or more co-additives, wherein the lubricating oil composition has greater than 50 ppm by mass of boron, less than 800 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, provided that the detergent additive composition comprises at least two detergents of at least two metals.
• the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 200 ppm or boron, less than 600 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, by mass ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 2 to 20 mass % of the additives.
• the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 300 ppm by mass of boron, less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, by mass ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 2 to 20 mass % of the additives.
• the invention provides an additive composition comprising, or made by admixing, a diluent or carrier oil, a boron-containing additive, a detergent additive composition comprising at least two detergents of at least two metals and one or more co-additives in such proportions so to provide a crankcase lubricating oil composition having greater than 50 ppm by mass of boron, less than 800 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, when the oil composition contains 2 to 20 mass % of the additives.
• the invention provides a method for conferring wear resistance to a crankcase lubricating oil composition that contains less than 900 ppm by mass of phosphorus and less than 6000, preferably less than 5000, such as less than 4000, ppm by mass of sulfur, based on the mass of the oil composition, by provision in the oil composition of a boron-containing additive to provide greater than 50 ppm by mass of boron based on the mass of the oil composition.
• the invention provides a method of lubricating the crankcase of a spark-ignited or a compression-ignited internal combustion engine which comprises supplying to the engine a lubricating oil composition according to the first, second or third aspect of the invention.
• the invention provides the use of an effective amount of a boron-containing additive in a crankcase lubricating oil composition that contains less than 900 ppm by mass of phosphorus and less than 6000 ppm by mass of sulfur, based on the mass of the oil composition, to provide wear resistance, in particular in the Peugeot TU3M Scuffing Test and/or Sequence IVA Test.
• An effective amount is preferably an amount sufficient to provide at least 50 ppm by mass of boron based on mass of the oil composition.
• the lubricating oil compositions of this invention comprise defined individual, i.e., separate, components that may or may not remain the same chemically before and after mixing.
• various components of the composition essential as well as optional and customary, may react under the conditions of formulation, storage or use, and that the invention also provides the product obtainable or obtained as a result of any such reaction.
• the amount of phosphorus, sulfur or boron in the lubricating oil composition is measured according to ASTM D5185.
• the amount of phosphorus in the lubricating oil composition is preferably less than 550, more preferably less than 500, such as less than 400, especially less than 300 or 200, advantageously less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
• the amount of phosphorus in the lubricating oil composition is preferably less than 800 or 700, more preferably less than 600 or 550, such as less than 500 or 400, especially less than 300 or 200, advantageously less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
• the amount of phosphorus in the lubricating oil composition is preferably less than 700, more preferably less than 600 or 550, such as less than 500 or 400, especially less than 300 or 200, advantageously less than 100, ppm, based on the mass of the oil composition. More preferably, it is zero.
• the amount of sulfur in the lubricating oil composition is preferably at most 5000 or 4000, or at most 3000 or 2500, ppm by mass, based on the mass of the oil composition; especially it is at most 2000, or at most 1500, ppm by mass; advantageously it is less than 1000, or less than 700, ppm. More preferably, it is zero.
• the phosphorus in the oil composition is derived from a phosphorus-containing additive, such as a ZDDP that may be present.
• the sulfur can be derived from the oil of lubricating viscosity, such as Group I, II or III basestock; the diluent oil or carrier oil, which is used as a carrier fluid for the additive components and additive compositions; and any sulfur-containing additives, for example, ZDDPs and sulfonate detergents.
• the defined amount of phosphorus is in respect of the amount of phosphorus derived from ZDDP that is present.
• the amount of boron, independently of the amount of sulfur or phosphorus, with respect to the first or fourth aspect is preferably greater than 250, for example, greater than 300, ppm, based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 400, 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200, 1500 or 2000, ppm.
• the amount of boron does not exceed 10,000, preferably not greater than 7500, more preferably not greater than 5000, such as not greater than 3000, ppm, based on the mass of the oil composition.
• the amount of boron, independently of the amount of sulfur or phosphorus, with respect to the second or fifth aspect is preferably greater than 350, for example, greater than 400, ppm, based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200, 1500 or 2000, ppm.
• the amount of boron does not exceed 10,000, preferably not greater than 7500, more preferably not greater than 5000, such as not greater than 3000, ppm, based on the mass of the oil composition.
• the amount of boron, independently of the amount of sulfur or phosphorus, with respect to the third, sixth, seventh or ninth aspect is preferably greater than 100, for example, greater than 200, ppm, based on the mass of the oil composition; more preferably the amount of boron is greater than any one of 300, 400, 500, 600, 700, 800 or 900, ppm; especially the amount of boron is greater than any one of 1000, 1100, 1200, 1500 or 2000, ppm.
• the amount of boron does not exceed 10,000, preferably not greater than 7500, more preferably not greater than 5000, such as not greater than 3000, ppm, based on the mass of the oil composition.
• the boron in the oil composition is derived from a boron-containing additive.
• one or more of a zinc dithiocarbamate and a copper-containing compound are substantially absent.
• a molybdenum-containing additive for example a molybdenum dithiocarbamate is present in the oil composition, then the amount of molybdenum in the oil composition is at most 1000, preferably at most 750, more preferably at most 500, such as at most 400, especially at most 300, advantageously at most 200, more advantageously at most 100, ppm by mass, based on the mass of the oil composition.
• the lubricating oil composition has less than 1.5, especially less than 1.3, such as in the range from 0.01 to 0.5, mass % of sulfated ash, according to the method ASTM D874.
• the lubricating oil composition is a multigrade identified by the viscometric descriptor SAE 15WX, SAE 10WX, SAE 5WX or SAE 0WX, where X represents any one of 20, 30, 40 and 50; the characteristics of the different viscometric grades can be found in the SAE J300 classification.
• the lubricating oil composition is in the form of an SAE 10WX, SAE 5WX or SAE 0WX, preferably in the form of an SAE 5WX or SAE 0WX, wherein X represents any one of 20, 30, 40 and 50.
• X is 20 or 30.
• the lubricating oil compositions of each aspect of the invention are suitable for lubricating an internal combustion engine, such as a passenger car engine or a heavy duty diesel engine.
• passenger car engines are light duty diesel engines and gasoline engines.
• the heavy duty diesel engines are used in land-based vehicles, preferably large road vehicles, such as large trucks.
• the road vehicles typically have a weight greater than 12 tonnes.
• the engines used in such vehicles tend to have a total displacement of at least 6.5, preferably at least 8, more preferably at least 10, such as at least 15, litres; engines having a total displacement of 12 to 20 litres are preferred.
• engines having a total displacement greater than 24 litres are not considered land-based vehicles.
• the engines according to the present invention also have a displacement per cylinder of at least 1.0 or at least 1.5, such as at least 1.75, preferably at least 2, litres per cylinder.
• heavy duty diesel engines in road vehicles have a displacement per cylinder of at most 3.5, such as at most 3.0; preferably at most 2.5, litres per cylinder.
• the terms 'total displacement' and 'displacement per cylinder' are known to those skilled in the art of internal combustion engines (see “Diesel Engine Reference Book", edited by B. Challen and R. Baranescu, second edition, 1999, published by SAE International). Briefly, the term “displacement' corresponds to the volume of the cylinder in the engine as determined by the piston movement and consequently the “total displacement” is the total volume dependent on the number of cylinders; and the term 'displacement per cylinder' is the ratio of the total displacement to the number of cylinders in the engine.
• the present invention provides a combination of a heavy duty diesel engine in a land-based vehicle which engine has a total displacement of at least 6.5 litres and a displacement per cylinder of at least 1.0 litre per cylinder and a lubricating oil composition as defined in any one of the first, second or third aspect.
• API American Petroleum Institute
• API Association des Constructeur Europeén d'Autombile
• JASO Japanese Standards Organisation
• Global which contains tests and performance levels from ACEA, API and JASO specifications.
• a heavy duty lubricating oil composition of the present invention preferably satisfies at least the performance requirements of heavy duty diesel engine lubricants, such as at least the API CG-4; preferably at least the API CH-4; especially at least the API CI-4.
• the lubricating oil composition of the invention independently of meeting the API performance requirements, preferably satisfies at least the ACEA E2-96; more preferably at least the ACEA E3-96; especially at least ACEA E4-99; advantageously at least the ACEA E5-99.
• the lubricating oil composition of the invention, independently of meeting the API and ACEA performance requirements preferably satisfies the JASO DH-1 or Global DHD-1.
• the lubricating oil composition preferably satisfies at least the performance requirements of API SH; more preferably at least the API SJ; especially at least the API SL.
• the lubricating oil composition of the invention independently of meeting the API performance requirements, preferably satisfies at least the ACEA A2-96 (issue 2), more preferably at least the ACEA A3-98, especially at least the ACEA A1-98, for gasoline engines; and at least ACEA B2-98, more preferably at least the ACEA B1-98, such as at least the ACEA B3-98, especially at least the ACEA B4-98, for light duty diesel engines.
• the oil of lubricating viscosity or lubricating oil can be a synthetic or mineral oil of lubricating viscosity selected from the group consisting of Group I, II, III, IV and V basestocks, and a mixture containing any two or more thereof.
• Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
• API 1509 "Engine Oil Licensing and Certification System” Fourteenth Edition, December 1996 states that all basestocks are divided into five general categories:
• the lubricating oil is selected from any one of Group I to V basestocks and mixtures thereof.
• test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
• Boron-containing additives may be prepared by reacting a boron compound with an oil-soluble or oil-dispersible additive or compound.
• Boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acid such as boronic acid, boric acid, tetraboric acid and metaboric acid, boron hydrides, boron amides and various esters of boron acids.
• boron-containing additives include a borated dispersant; a borated dispersant VI improver; an alkali metal or a mixed alkali metal or an alkaline earth metal borate; a borated overbased metal detergent; a borated epoxide; a borate ester; and a borate amide.
• Borated dispersants may be prepared by boration of succinimide, succinic ester, benzylamine and their derivatives, each of which has an alkyl or alkenyl group of molecular weight of 700 to 3000. Processes for manufacture of these additives are known to those skilled in the art. A preferred amount of boron contained in these dispersants is 0.1 to 5 mass % (especially 0.2 to 2 mass %). A particularly preferable borated dispersant is a succinimide derivative of boron, for example borated polyisobutenyl succinimide.
• Alkali metal and alkaline earth metal borates are generally hydrated particulate metal borates, which are known in the art.
• Alkali metal borates include mixed alkali and alkaline earth metal borates. These metal borates are available commercially.
• Representative patents describing suitable alkali metal and alkaline earth metal borates and their methods of manufacture include U.S. 3,997,454; 3,819,521; 3,853.772; 3,907,601; 3,997,454; and 4,089,790.
• Boron-containing additives include borated fatty amines.
• the borated amines may be prepared by reacting one or more of the above boron compounds with one or more of fatty amines, e.g., an amine having from four to eighteen carbon atoms. They may be prepared by reacting the amine with the boron compound at a temperature in the range of from 50 to 300, preferably from 100 to 250, °C, and at a ratio from 3:1 to 1:3 equivalents of amine to equivalents of boron compound.
• Borated fatty epoxides are generally the reaction product of one or more of the above boron compounds with at least one epoxide.
• the epoxide is generally an aliphatic epoxide having from 8 to 30, preferably from 10 to 24, more preferably from 12 to 20, carbon atoms.
• Examples of useful aliphatic epoxides include heptyl epoxide and octyl epoxide. Mixtures of epoxides may also be used, for instance commercial mixtures of epoxides having from 14 to 16 carbon atoms and from 14 to 18 carbon atoms.
• the borated fatty epoxides are generally known and are described in U.S. Patent 4,584,115.
• Borate esters may be prepared by reacting one or more of the above boron compounds with one or more alcohols of suitable oleophilicity. Typically, the alcohols contain from 6 to 30, or from 8 to 24, carbon atoms. The methods of making such borate esters are known in the art.
• the borate esters can be borated phospholipids. Such compounds, and processes for making such compounds, are described in EP-A-0 684 298.
• Borated overbased metal detergents are known in the art where the borate substitutes the carbonate in the core either in part or in full.
• a preferred boron-containing additive is a borated polyisobutenyl succinimide wherein the average number molecular weight ( M n) of the polybutenyl backbone is in the range from 700 to 1250.
• a detergent additive composition which comprises one or more detergents, may be provided in the lubricating oil composition.
• a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is usually based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
• Organic acids useful in present invention typically have one or more functional groups, such as OH or COOH or SO 3 H, and a hydrocarbyl substituent. Examples of organic acids include sulfonic acids, phenols and sulfurised derivatives thereof, and carboxylic acids.
• the metal detergent may be neutral or overbased, which terms are known in the art.
• the detergent additive composition may comprise one or more neutral detergents or one or more overbased detergents or a mixture thereof.
• the metals are preferably selected from Group 1 and Group 2 metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
• the detergent additive composition in respect of each aspect of the invention, comprises a metal salt of an aromatic carboxylic acid, for example a salicylate-based detergent, such as calcium salicylate.
• the detergent additive composition comprises more than 50 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition. More preferably the proportion of the metal salt of an aromatic carboxylic acid is at least 60 or at least 70 mole %; more preferably at least 80 or at least 90 mole %, based on the moles of the metal salts of organic acids in the detergent additive composition.
• the detergent additive composition comprises 100 mole % of a metal salt of an aromatic carboxylic acid, based on the moles of the metal salts of organic acids in the detergent composition, that is the detergent additive composition comprises only aromatic carboxylic acids as the organic acids.
• aromatic carboxylic acids are salicylic acids and sulphurised derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof. Especially preferred are salicylic acids.
• the detergent additive composition comprises one or more detergents of the same metal, for example calcium or magnesium, preferably calcium; more preferably the detergents are of different surfactant types, such as calcium salicylate and calcium sulfonate.
• the detergent additive composition comprises at least two detergents of at least different two metals, for example a neutral or overbased magnesium detergent and at least one other metal detergent, e.g., a neutral or overbased calcium detergent and/or neutral or overbased sodium detergent.
• Preferred detergent additive compositions in respect of each aspect of the invention comprise a mixture of calcium and magnesium detergents.
• Detergent additive compositions comprising only salicylate detergents, whether neutral or overbased, are particularly advantageous.
• Surfactants that may also be used include aliphatic carboxylates; sulfonates; phenates, non-sulfurised or sulfurised; thiophosphonates; and naphthenates.
• a detergent in the form of a hybrid complex detergent wherein the basic material is stabilised by more than one type of surfactant.
• a single type of organic acid may contain a mixture of organic acids of the same type.
• a sulphonic acid may contain a mixture of sulphonic acids of varying molecular weights.
• Such an organic acid composition is considered as one type.
• complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate detergent.
• EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates"
• the proportion of one surfactant to another in a complex detergent is not critical.
• Preferred complex detergents are salicylate-based detergents, for example, "phenalates” and salicylate-based detergents disclosed in any one of International Patent Application Publication Nos. 9746643/4/5/6 and 7.
• the detergents can have a Total Base Number (TBN) in the range of 15 or 60 to 600, preferably 100 to 450, more preferably 160 to 400.
• TBN Total Base Number
• the detergent additive composition consists of metal salicylate detergents
• the salicylate is either calcium salicylate or a mixture of calcium and magnesium salicylates. More preferably, at least one or each metal salicylate detergent is overbased.
• both calcium and magnesium salicylates are present, more calcium salicylate than magnesium salicylate is preferably be present, based on the mass of the respective metals.
• the detergent additive composition comprises two or more metal detergents of different surfactant types, it is preferred that the detergents have the same metal, for example, calcium.
• the total amount of metal derived from the metal detergents in the lubricating oil composition is at most 2700 ppm, based on the mass of the oil composition.
• Suitable methods for measuring the total metal content are well known in the art and include X-ray fluorescence and atomic absorption spectrometry.
• Means for determining the amount of metal salt of an organic acid are known to those skilled in the art.
• a skilled person can calculate the amounts in the final lubricating oil composition from information concerning the amount of raw materials (e.g., organic acids) used to make the detergent(s) and from information concerning the amount of detergent(s) used in the final oil composition.
• Analytical methods e.g., potentiometric titration and chromatography
• can also be used to determine the amounts of metal salts of organic acid e.g., in the case of a metal sulphonate, ASTM D3712 may be used to determine the metal associated with the sulphonate).
• co-additives may be present to meet particular requirements.
• examples of such include viscosity index improvers, corrosion inhibitors, detergents other than those mentioned, metal rust inhibitors, pour point depressants, anti-foaming agents, dispersants other than those mentioned, anti-wear agents, oxidation inhibitors or anitoxidants, and friction modifiers.
• the preparation of an additive composition is a convenient method of adding the additives to a lubricating oil in order to yield a lubricating oil composition.
• the amount of additives in the final lubricating oil composition is generally dependent on the type of the oil composition, for example, a heavy duty diesel engine lubricating oil composition preferably has 7 to 20, more preferably 8 to 16, such as 8 to 14, mass % of additives, based on the mass of the oil composition.
• a passenger car engine lubricating oil composition for example, a gasoline or a diesel engine oil composition, tends to have a lower amount of additives, for example 2 to 10, such as 3 or 4 to 10, preferably 3 to 9, especially 6 to 8, mass % of additives, based on the mass of the oil composition.
• the sulfated ash content of each composition is on or about 1 mass %.

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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)

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• 2002
  • 2002-01-14 EP EP02250224A patent/EP1329496A1/fr not_active Withdrawn

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