EP1757673A1 - Composition lubrifiante pour un moteur à combustion interne - Google Patents

Composition lubrifiante pour un moteur à combustion interne Download PDF

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Publication number
EP1757673A1
EP1757673A1 EP05255181A EP05255181A EP1757673A1 EP 1757673 A1 EP1757673 A1 EP 1757673A1 EP 05255181 A EP05255181 A EP 05255181A EP 05255181 A EP05255181 A EP 05255181A EP 1757673 A1 EP1757673 A1 EP 1757673A1
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Prior art keywords
lubricating oil
oil composition
composition according
sulfur
phosphorus
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EP05255181A
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German (de)
English (en)
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EP1757673B1 (fr
Inventor
Alexander B. Boffa
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular 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
    • 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary 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
    • 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
    • C10M2215/08—Amides
    • 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
    • C10M2215/086—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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • 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
    • 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
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/063—Ammonium or amine 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
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10N2030/24—Emulsion properties
    • 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
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

  • ILSAC International Lubricant Standardization and Approval Committee
  • the ILSAC GF-4 specifies the minimum performance requirements (both engine sequence and bench tests) and chemical and physical properties for those engine oils that vehicle manufacturers deem necessary for satisfactory equipment performance and life.
  • Such catalytic converters generally use a combination of catalytic metals, e.g., platinum or variations, and metal oxides, and are installed in the exhaust streams, e.g., the exhaust pipes of automobiles, to convert the toxic gases to nontoxic gases.
  • these catalyst components are poisoned by the phosphorus and sulfur components, or the phosphorus and sulfur decomposition product of the zinc dialkyldithiophosphate; and accordingly, the use of engine oils containing phosphorus and sulfur additives may substantially reduce the life and effectiveness of catalytic converters. Therefore, it would be desirable to reduce the phosphorus and sulfur content in the engine oils so as to maintain the activity and extend the life of the catalytic converter.
  • the present invention relates to a lubricating oil composition for internal combustion engines which demonstrates improved fuel economy. More particularly, the present invention relates to a low phosphorus lubricating oil composition employing a base oil of lubricating viscosity, a sulfonate detergent, oxymolybdenum-containing complex, a friction modifier and an antioxidant to achieve the fuel economy benefits demonstrated in the lubricating oil composition while also providing high temperature oxidation, piston deposits, and wear.
  • the lubricating oil composition of the present invention may further contain an oil-soluble, phosphorus-containing, anti-wear compound and an alkenyl succinimide dispersant derived from a 450 to 3000 average molecular weight polyalkylene.
  • the lubricating oil composition of the present invention provides improved fuel economy while also providing high temperature oxidation, piston deposits, and wear. Accordingly, the present invention is further directed to a method for improving the fuel economy of an internal combustion engine, preferably gasoline, comprising operating said engine with the lubricating oil composition of the present invention.
  • alkaline earth metal means calcium, barium, magnesium, strontium, or mixtures thereof.
  • hydrocarbyl means an alkyl or alkenyl group.
  • metal means alkali metals, alkaline earth metals, or mixtures thereof.
  • the acids obtained by sulfonation are converted to the metal salts by neutralizing with a basic reacting alkali or alkaline earth metal compound to yield the Group I or Group II metal sulfonates.
  • the acids are neutralized with an alkali metal base.
  • Alkaline earth metal salts are obtained from the alkali metal salt by metathesis.
  • the sulfonic acids can be neutralized directly with an alkaline earth metal base.
  • the sulfonates may then be overbased and such overbased materials and methods of preparing such materials are known to those skilled in the art. See, for example, LeSuer U.S. Pat. No. 3,496,105, issued Feb. 17, 1970 , particularly Cols. 3 and 4.
  • the sulfonates are present in the lubricating oil composition of the present invention in the form of alkaline earth metal salts, or mixtures thereof.
  • the alkaline earth metals include magnesium, calcium and barium, of which calcium is preferred.
  • the sulfonates are superalkalinized employing excess alkaline metal base carbon dioxide or other suitable base source. Often this is added sequentially or step wise addition with or without a promoter, paying particular attention to the overbasing process since improper overbasing will lead to highly viscous sulfonates or lower overbased than desired.
  • the oil-soluble overbased alkaline earth metal alkyl aryl sulfonate detergents are overbased under suitable conditions to substantially produce from about 25 to 500 TBN, preferably from about 250 to 500 TBN, and most preferably from about 300 to 450 TBN.
  • TBN can be measured according to ASTM D2986.
  • Particularly preferred for overbasing are calcium oxide and/or calcium hydroxide with carbon dioxide to produce an overbased calcium sulfonate.
  • synthetic alkyl aryl sulfonates are also preferred. Particularly useful are synthetic alkyl aryl sulfonates having the aryl sulfonate attached at the 1 or 2 position of the alkyl group, preferably greater than 5 mole %, more preferably greater than 13 mole % and more preferably greater than 20 mole %, as these have shown good compatibility and solubility while not forming a skin at these levels of overbasing. Preferred are linear monoalkyl sulfonates.
  • the overbased alkaline earth metal alkyl aryl sulfonate detergent will generally have a TBN from about 25 to 500, preferably 250 to 500, and more preferably 300 to 450.
  • the basic nitrogen compound used to prepare the oxymolybdenum complexes have at least one basic nitrogen and are preferably oil-soluble.
  • Typical examples of such compositions are succinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbon polyamines, Mannich bases, phosphoramides, thiophosphoramides, phosphonamides, dispersant viscosity index improvers, and mixtures thereof.
  • Any of the nitrogen-containing compositions may be after-treated with, e.g., boron, using procedures well known in the art so long as the compositions continue to contain basic nitrogen. These after-treatments are particularly applicable to succinimides and Mannich base compositions.
  • Mannich bases prepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms with formaldehyde and an alkylene polyamine HN(ANH) n H where A is a saturated divalent alkyl hydrocarbon of from about 2 to 6 carbon atoms and n is from about 1-10 and where the condensation product of said alkylene polyamine may be further reacted with urea or thiourea.
  • A is a saturated divalent alkyl hydrocarbon of from about 2 to 6 carbon atoms and n is from about 1-10 and where the condensation product of said alkylene polyamine may be further reacted with urea or thiourea.
  • the utility of these Mannich bases as starting materials for preparing lubricating oil additives can often be significantly improved by treating the Mannich base using conventional techniques to introduce boron into the composition.
  • compositions useful for preparing the oxymolybdenum complexes employed in this invention are the phosphoramides and phosphonamides such as those disclosed in U.S. Pat. Nos. 3,909,430 and 3,968,157 , the disclosures of which are hereby incorporated by reference.
  • These compositions may be prepared by forming a phosphorus compound having at least one P-N bond. They can be prepared, for example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a mono-functional amine.
  • Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from about 2 to 450 or more carbon atoms, such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, and the like, with phosphorus pentasulfide and a nitrogen-containing compound as defined above, particularly an alkylamine, alkyldiamine, alkylpolyamine, or an alkyleneamine, such as ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like.
  • an unsaturated hydrocarbon compound containing from about 2 to 450 or more carbon atoms
  • an unsaturated hydrocarbon compound containing from about 2 to 450 or more carbon atoms such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene
  • sulfurizing agents are traditional sulfur-containing antioxidants such as wax sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic and esters and sulfurized ester-olefins, and sulfurized alkylphenols and the metal salts thereof.
  • mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils, such as tall oil, linseed oil, olive oil, caster oil, peanut oil, rape oil, fish oil, sperm oil, and so forth.
  • Exemplary fatty esters include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, and alkyl glycerides.
  • Cross-sulfurized ester olefins such as a sulfurized mixture of C 10 -C 25 olefins with fatty acid esters of C 10 -C 25 fatty acids and C 10 -C 25 alkyl or alkenyl alcohols, wherein the fatty acid and/or the alcohol is unsaturated may also be used.
  • Sulfurized olefins are prepared by the reaction of the C 3 -C 6 olefin or a low-molecular-weight polyolefin derived therefrom with a sulfur-containing compound such as sulfur, sulfur monochloride, and/or sulfur dichloride.
  • aromatic and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax-olefin sulfides and so forth.
  • They can be prepared by treating the starting material, e.g., olefinically unsaturated compounds, with sulfur, sulfur monochloride, and sulfur dichloride.
  • the paraffin wax thiomers described in U.S. Pat. No. 2,346,156 .
  • Sulfurized alkyl phenols and the metal salts thereof include compositions such as sulfurized dodecylphenol and the calcium salts thereof.
  • the alkyl group ordinarily contains from about 9 to 300 carbon atoms.
  • the metal salt may be preferably, a Group I or Group II salt, especially sodium, calcium, magnesium, or barium.
  • the polar promoter is separately added to the reaction mixture, it may also be present, particularly in the case of water, as a component of non-anhydrous starting materials or as waters of hydration in the acidic molybdenum compound, such as (NH 4 ) 6 Mo 7 O 24 ⁇ H 2 O. Water may also be added as ammonium hydroxide.
  • This reaction mixture may optionally be treated with a sulfur source as defined above at a suitable pressure and temperature for the sulfur source to react with the acidic molybdenum and basic nitrogen compounds. In some cases, removal of water from the reaction mixture may be desirable prior to completion of reaction with the sulfur source.
  • the preparation of the sample for color measurement comprises diluting the molybdenum-containing composition with isooctane to achieve a constant molybdenum concentration of 0.00025 g molybdenum per gram of the molybdenum-containing composition/isooctane mixture.
  • the spectrophotometer Prior to sample measurement the spectrophotometer is referenced by scanning air versus air. The UV visible spectrum from 350 nanometers to 900 nanometers is obtained using a one centimeter path-length quartz cell versus an air reference. The spectra are offset corrected by setting the 867 nanometer absorbance to zero. Then the absorbance of the sample is determined at 350 nanometers wavelength.
  • Friction modifiers include such compounds as aliphatic carboxylic acids, aliphatic carboxylic esters of polyols such as glycerol esters of fatty acid as exemplified by glycerololeate, boric esters of glycerol fatty acid monoesters, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
  • 4,530,771 and 5,629,272 which is a preferred borated glycerol monooleate comprising esters constituted with a glycerol, fatty acid and a boric acid, said ester having a positive amount up to 2.0 moles of a carboxylic acid residue comprising a saturated or unsaturated alkyl group having from about 8 to 24 carbon atoms and from about 1.5 to 2.0 moles of a glycerol residue, both per unit mole of a boric acid residue on average of the boric esters used singly or in combination, molar proportion between said carboxylic acid residue and said glycerol residue being that the glycerol residue is 1.2 moles or more based on 1 mole of the carboxylic acid residue;
  • U.S. Pat. No. 3,779,928 which discloses alkane phosphonic acid salts, the disclosure which is herein incorporated by reference.
  • the friction modifier employed in the lubricating oil composition of the present invention is an ester of a carboxylic acid and a polyhydric alcohol such as those disclosed in U.S. Pat. No. 6,203,584 , which is hereby incorporated by reference for all purposes.
  • the ester component employed in the present fuel composition is an ester of a carboxylic acid and a polyhydric alcohol, wherein the carboxylic acid has from one to about four carboxylic acid groups and from about 8 to about 50 carbon atoms and the polyhydric alcohol has from about 2 to about 50 carbon atoms and from about 2 to about 6 hydroxy groups.
  • saturated monocarboxylic acids include those having from about 10 to about 22 carbon atoms, such as capric, lauric, myristic, palmitic, stearic and behenic acid.
  • unsaturated monocarboxylic acids include those having from about 10 to about 22 carbon atoms, such as oleic, elaidic, palmitoleic, petroselic, eleostearic, linoleic, linolenic, erucic and hypogaeic acid.
  • the carboxylic acid is oleic acid.
  • Suitable polyhydric alcohols include dihydroxy alcohols, such as the alkylene glycols, for example, ethylene glycol and propylene glycol, trihydroxy alcohols, such as glycerol, tetrahydroxy alcohols, such as pentaerythritol, and hexahydroxy alcohols, such as sorbitol.
  • dihydroxy alcohols such as the alkylene glycols, for example, ethylene glycol and propylene glycol
  • trihydroxy alcohols such as glycerol
  • tetrahydroxy alcohols such as pentaerythritol
  • hexahydroxy alcohols such as sorbitol.
  • the ester may have one or more free hydroxy groups.
  • Boric acid derivatives of the ester of the carboxylic acid and polyhydric alcohol are particularly useful in the lubricating oil composition of the present invention.
  • Suitable boric acid esters are disclosed in U.S. Pat. Nos. 4,530,771 and 5,629,272 , cited above, which is hereby incorporated in its entirety by reference for all purposes.
  • the friction modifier employed in the lubricating oil of the present invention is borated glycerol monooleate.
  • the friction modifier is incorporated in the lubricating oil composition of the present invention in an amount of from about 0.1 to 5 wt. %, based on the total weight of the lubricating oil composition. Preferably, from about 0.2 to 1.5 wt %, based on the total weight of the lubricating oil composition, of the friction modifier may be used.
  • An oxidation inhibitor or antioxidant is employed in the lubricating oil composition of the present invention.
  • Antioxidants reduce the tendency of base stocks to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • the antioxidant employed in the lubricating oil of the present invention may also be a sulfur-containing compound such as, but is not limited to, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfides, ashless oil-soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, wax sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acids and esters, sulfurized ester-olefins, sulfurized alkylphenols, phosphorus esters, metal thiocarbamates or dithiocarbamates wherein the metal is zinc, copper or molybdenum, ashless thiocarbamates or dithiocarbamates (i.e., essentially metal free) such as methylenebis(dialkyldithiocarbamate), ethylenebis(dialkyldithiocarbamate), and isobuty
  • the antioxidant comprises from about 0.2 to 10 wt % and preferably 0.5 to 2.5 wt %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition of the present invention is notably effective at reducing deposits when the total concentration of the oxymolybdenum-containing complex and the antioxidant is at least 1.3 wt %, preferably at least 1.45 wt %, based on the total weight of the lubricating oil composition.
  • Such compounds may be prepared in accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol or a phenol with P 2 S 5 and then neutralizing the dithiophosphoric acid with a suitable zinc compound.
  • Mixtures of alcohols may be used including mixtures of primary and secondary alcohols. Examples of such alcohols include, but are not restricted to the following list: iso-propanol, iso-octanol, 2-butanol, methyl isobutyl carbinol (4-methyl-1-pentane-2-ol), 1-pentanol, 2-methyl butanol, and 2-methyl-1-propanol.
  • the hydrocarbyl groups can be a primary, secondary, or mixtures thereof, e.g. the compounds may contains primary and/or secondary alkyl groups derived from primary or secondary carbon atoms. Moreover, when employed, there is preferably at least 50, more preferably 75 or more, most preferably from about 85 to 100, mass % secondary alkyl groups; an example is a ZDDP having 85 mass % secondary alkyl groups and 15 mass % primary alkyl groups, such as a ZDDP made from 85 mass % butan-2-ol and 15 mass % iso-octanol. Even more preferred is a ZDDP derived from derived from sec-butanol and methylisobutylcarbinol and most preferably wherein the sec-butanol is 75 mole percent.
  • the oil-soluble, phosphorus-containing, anti-wear compound comprises from about 0.1 to 2.0 wt % and preferably 0.25 to 1.2 wt %, based on the total weight of the lubricating oil composition.
  • a dispersant may also be employed in the lubricating oil composition of the present invention.
  • the dispersant may be ashless dispersants such as an alkenyl succinimide, an alkenyl succinic anhydride, an alkenyl succinate ester, and the like, or mixtures of such dispersants.
  • Ashless dispersants are broadly divided into several groups.
  • One such group is directed to copolymers which contain a carboxylate ester with one or more additional polar function, including amine, amide, imine, imide, hydroxyl carboxyl, and the like. These products can be prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above function.
  • Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethyl methacrylate copolymers and the like.
  • amides and polyamides or esters and polyesters such as tetraethylene pentamine, polyvinyl polysterarates and other polystearamides may be employed.
  • Preferred dispersants are N-substituted long chain alkenyl succinimides.
  • Mono and bis alkenyl succinimides are usually derived from the reaction of alkenyl succinic acid or anhydride and alkylene polyamines. These compounds are generally considered to have the formula wherein R 2 is a substantially hydrocarbon radical having a molecular weight from about 450 to 3000, that is, R 2 is a hydrocarbyl radical, preferably an alkenyl radical, containing from about 30 to about 200 carbon atoms; Alk is an alkylene radical of from about 2 to 10, preferably from about 2 to 6, carbon atoms, R 3 , R 4 , and R 5 are selected from a C 1 -C 4 alkyl or alkoxy or hydrogen, preferably hydrogen, and x is an integer from about 0 to 10, preferably from about 0 to 3.
  • the actual reaction product of alkylene or alkenylene succinic acid or anhydride and alkylene polyamine will comprise the mixture of compounds including succinamic acids and succinimides. However, it is customary to designate this reaction product as a succinimide of the described formula, since this will be a principal component of the mixture.
  • the mono alkenyl succinimide and bis alkenyl succinimide produced may depend on the charge mole ratio of polyamine to succinic groups and the particular polyamine used. Charge mole ratios of polyamine to succinic groups of about 1:1 may produce predominately mono alkenyl succinimide. Charge mole ratios of polyamine to succinic group of about 1:2 may produce predominately bis alkenyl succinimide.
  • N-substituted alkenyl succinimides can be prepared by reacting maleic anhydride with an olefinic hydrocarbon followed by reacting the resulting alkenyl succinic anhydride with the alkylene polyamine.
  • the R 2 radical of the above formula that is, the alkenyl radical, is preferably derived from a polymer prepared from an olefin monomer containing from about 2 to 5 carbon atoms.
  • the alkenyl radical is obtained by polymerizing an olefin containing from about 2 to 5 carbon atoms to form a hydrocarbon having a molecular weight ranging from about 450 to 3000.
  • Such olefin monomers are exemplified by ethylene, propylene, 1-butene, 2-butene, isobutene, and mixtures thereof.
  • the alkenyl succinimide may be prepared by reacting a polyalkylene succinic anhydride with an alkylene polyamine.
  • the polyalkylene succinic anhydride is the reaction product of a polyalkylene (preferably polyisobutene) with maleic anhydride.
  • a polyalkylene preferably polyisobutene
  • maleic anhydride preferably polyisobutene
  • One can use thermal, chlorination, free radical, acid catalyzed, or any other process in this preparation.
  • suitable polyalkylene succinic anhydrides are thermal PIBSA (polyisobutenyl succinic anhydride) described in U.S. Pat.
  • the polyalkylene succinic anhydride is preferably a polyisobutenyl succinic anhydride.
  • the polyalkylene succinic anhydride is a polyisobutenyl succinic anhydride having a number average molecular weight of at least 450, more preferably at least from about 900 to 3000 and still more preferably from at least from about 900 to 2300.
  • a mixture of polyalkylene succinic anhydrides is employed.
  • the mixture preferably comprises a low molecular weight polyalkylene succinic anhydride component and a high molecular weight polyalkylene succinic anhydride component.
  • the low molecular weight component has a number average molecular weight of from about 450 to below 1000 and the high molecular weight component has a number average molecular weight of from about 1000 to about 3000.
  • both the low and high molecular weight components are polyisobutenyl succinic anhydrides.
  • various molecular weights polyalkylene succinic anhydride components can be combined as a dispersant as well as a mixture of the other above referenced dispersants as identified above.
  • the polyalkylene succinic anhydride can also be incorporated with the detergent which is anticipated to improve stability and compatibility of the detergent mixture.
  • the detergent When employed with the detergent it can comprise from about 0.5 to 5.0 percent by weight of the detergent mixture and preferably from about 1.5 to 4.0 wt %.
  • the preferred polyalkylene amines used to prepare the succinimides are of the formula: wherein z is an integer of from about 0 to 10 and Alk, R 3 , R 4 , and R 5 are as defined above.
  • the alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and also the cyclic and the higher homologs of such amines as piperazine and amino alkylsubstituted piperazines.
  • ethylene diamine triethylene tetraamine, propylene diamine, decamethyl diamine, octamethylene diamine, diheptamethylene triamine, tripropylene tetraamine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, ditrimethylene triamine, 2-heptyl-3-(2-aminopropyl)-imidazoline,4-methyl imidazoline, N,N-dimethyl-1,3-propane diamine, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful.
  • ethylene amines are especially useful. They are described in some detail under the heading " Ethylene Amines” in Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898-905 (Interscience Publishers, New York, 1950 ).
  • ethylene amine is used in a generic sense to denote a class of polyamines conforming for the most part to the structure H 2 N(CH 2 CH 2 NH) a H wherein a is an integer from 1 to 10.
  • the carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutenes having a molecular weight of from about 450 to 3000, preferably from about 900 to 2500, more preferably from about 1300 to 2300, and preferably from about 2000 to 2400, as well as mixtures of these molecular weights.
  • it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as taught in U.S. Pat. No. 5,716,912 incorporated herein by reference.
  • the dispersant when employed in the lubricating oil composition of the present invention comprises from about 2.0 to 10 wt %, preferably 3.0 to 5.0 wt %, based on the total weight of the lubricating oil composition.
  • the base oil of this invention may be any natural or synthetic lubricating base oil fraction particularly those having a kinematic viscosity at 100 degrees Centigrade (C) and about 4 centistokes (cSt) to about 20 cSt.
  • Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene, i.e., polyalphaolefin or PAO, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fisher-Tropsch process.
  • a preferred base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity about 20 cSt or higher at about 100 degrees C.
  • the base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.
  • Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
  • Suitable base oils include those in all API categories I, II, III, IV and V as defined in API Publication 1509, 14th Edition, Addendum I, December 1998, which is herein incorporated for all purposes. Saturates levels and viscosity indices for Group I, II and III base oils are listed in Table 1.
  • Group IV base oils are polyalphaolefins (PAO).
  • Synthetic oils may include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and inter-polymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogues and homologues thereof, and the like.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
  • Tri-alkyl phosphate ester oils such as those exemplified by tri-n-butyl phosphate and tri-iso-butyl phosphate are also suitable for use as base oils.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
  • Suitable purification techniques include distillation, hydrocracking, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Rerefined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • Base oil derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base oil.
  • Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
  • a major amount of base oil of lubricating viscosity as defined herein comprises 40 wt % or more, preferably about 40 wt % to about 97 wt %, more preferably about 50 wt % to about 97 wt %, still more preferably about 60 wt % to about 97 wt % and most preferably about 80 wt % to about 95 wt % of the lubricating oil composition.
  • additive components are examples of some of the components that can be favorably employed in the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it:
  • the low phosphorus lubricating oil compositions of the present invention were prepared by blending together the following components to obtain a SAE 5W-20 viscosity grade formulation (Table 2).
  • Table 2 Lubricating Oil Compositions
  • the quantity of the components in the lubricating oil are expressed as wt % unless noted otherwise.
  • Components are:
  • the fuel economy performance was determined by engine testing using a shortened version of the Sequence VIB test entitled herein as the Sequence VIB screener.
  • the Sequence VIB (ASTM D6837) is an engine dynamometer test that measures a lubricant's ability to improve the fuel economy of passenger cars and light-duty trucks equipped with a low friction engine. The method compares the performance of a test lubricant to the performance of a baseline lubricant over five different stages of operation.
  • the standard Sequence VIB test incorporates a flush and run type procedure with each test consisting of two 5-stage fuel economy measurements on a baseline oil (BC), one at the beginning of the test (Phase I) and one at the end (Phase II). The test oil is evaluated in between the two baseline runs.
  • Passing criteria relates to the minimum % fuel economy improvement versus the ASTM baseline (reference oil BC) for SAE 0W-20 and 5W-20 viscosity grades is at least 2.4% minimum after Phase I (16 hours aging), 2.0% minimum for SAE 0W-30 and 5W30 viscosity grades and at least 1.3 % for all other SAE multiviscosity grades.
  • the results of the V!B screener tests are presented in Table 3. Higher % FEI values indicate improved fuel economy. Table 3. VIB Screener Test Results Oil % Fuel Economy Improvement (FEI) A (Reference) 1.73 B (Comparative) 2.32 C (Invention) 2.55
  • the following results in Table 4 provide evidence of the further benefits of the lubricating oil composition of the present invention.
  • the low phosphorus lubricating oil compositions were prepared by blending together the components in Table 4 to obtain a SAE 5W-30 viscosity grade formulation.
  • the TEOST MHT4 Thermo-oxidation Engine Oil Simulation Test Moderately High Temperature, trademark of the Tannas Company
  • the TEOST MHT4 is for measuring engine deposits at moderately high temperatures on a special test rod exposed to automotive engine oils. In this test, a sample of the test engine oil containing a small amount of an organo-metallic catalyst is continuously cycled to flow down the outside of a pre-weighed, special wire-wound depositor rod positioned in a glass-mantle casing by two metal end caps.
  • the rod is resistively heated to obtain a constant temperature at the "hot spot" of 285°C for 24 hours. During this time, dry air is forces to flow through the mantle chamber at a specific rate of 10 mL/min.
  • the depositor rod is carefully rinsed of oil residue using a volatile hydrocarbon solvent and any deposits flaking off the rod while being washed are caught and filtered. After drying the rod and filter, the mass of deposits on the rod and in the filter are determined. The mass of deposits on the rod plus the mass of deposits on the filter is the total rod deposit mass.
  • the pass limit is 35 mg or less based on the ILSAC GF-4 specification. Table 4.
  • the balance of the lubricating oil composition contains a Group II base oil and minor other components such as foam inhibitors, viscosity index improvers, pour point depressants, dispersants, low overbased detergent, mixture of primary and secondary zinc dialkyldithiophosphates providing less than 0.08 wt % phosphorus content, based on the total weight of oil lubricating oil composition.
  • HOB Phenate Sequence VIB Screener Test Component a Oil H Oil I HOB Detergent @ 55 milliMoles Ca Sulfonate Ca Phenate Oxymolybdenum complex 0.5 0.5 Friction Modifier 0.5 0.5 Diphenylamine-type Antioxidant 0.4 0.4 VIB Screener Fuel economy, % FEI 2.45 2.08 a The quantity of the components in the lubricating oil are expressed as wt % unless noted otherwise. Components are:
  • the balance of the lubricating oil composition contains a Group II base oil and minor other components such as foam inhibitors, viscosity index improvers, pour point depressants, dispersants, sulfur-containing antioxidants, mixture of primary and secondary zinc dialkyldithiophosphates providing less than 0.08 wt % phosphorus content, based on the total weight of oil lubricating oil composition.
  • the total concentration of the oxymolybdenum-containing complex and antioxidant must be at least 1.3 wt %, based on the total weight of the lubricating oil composition.
  • Table 6 shows results demonstrating that a concentration of oxymolybdenum-containing complex and antioxidant of at least 1.3 wt % does not pass the ASTM Sequence IIIG/Mini Rotary Viscometer (MRV) used oil (ASTM D4684) test.
  • MMV Sequence IIIG/Mini Rotary Viscometer
  • the low phosphorus lubricating oil compositions were prepared by blending together the components in Table 6 to obtain a SAE 5W-30 viscosity grade formulation.
  • the balance of the lubricating oil composition contains a Group II base oil and minor other components such as foam inhibitors, viscosity index improvers, pour point depressants, phenates, mixture of primary and secondary zinc dialkyldithiophosphates providing less than 0.08 wt % phosphorus content, based on the total weight of oil lubricating oil composition.
  • the lubricating oil composition (Oil J) fails the MRV test when the total concentration of the oxymolybdenum-containing complex and the antioxidant is below 1.3 wt %, based on the total weight of the lubricating oil composition.
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CN106635281B (zh) * 2016-09-20 2020-05-19 中国石油化工股份有限公司 内燃机车油组合物及其用途
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