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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or 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
  • 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
  • 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
  • C10M2215/28—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
  • C10M2219/02—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
• • 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
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/061—Esters derived from boron
  • C10M2227/062—Cyclic esters
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/38—Catalyst protection, e.g. in exhaust gas converters
• • 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

Definitions

• the disclosed technology relates to a lubricating oil composition and to a method of improving the efficiency of the emissions control system of an internal combustion engine.
• the lubricating oil composition may be characterized by the inclusion of at least one overbased low molecular weight zinc dialkyldithiophosphate.
• the method relates to using the lubricating oil composition to lubricate an internal combustion engine equipped with the exhaust gas after treatment device.
• the exhaust gas after treatment device comprises a catalyst and the contamination of the catalyst is reduced.
• ZDDPs zinc dialkyldithiophosphat.es
• EP extreme pressure
• antiwear additives in engine oils.
• phosphorus concentration has been reduced for some SAE passenger car engine oil classifications.
• ILSAC GF-1 phosphorus levels were limited to no more than 1200 parts per million (ppm) and with GF-3 to 1000 ppm. Even at these levels of phosphorus, however, catalyst contamination is still an issue. The problem therefore is to provide adequate engine lubrication and at the same time reduce catalyst contamination.
• the disclosed technology in at least one embodiment, provides a solution to this problem. Summary of the Invention
• the disclosed technology relates to a lubricating oil composition
• a lubricating oil composition comprising at least one base oil and at least one overbased low molecular weight zinc dialkyldithiophosphate derived from one or more dithiophosphoric acids represented by the formula -SH (I) and/or metal salt thereof, wherein in formula (I), R 1 and R 2 are independently hydrocarbyl groups, the average total number of carbon atoms in R 1 and R 2 in formula (I) being in the range from 4 to 10, the metal ratio for the overbased low molecular weight zinc dialkyldithiophosphate being at least about 1.15:1 , the lubricating oil composition being characterized by a phosphorus concentration of up to about 0.12% by weight.
• the disclosed technology relates to a method of lubricating an internal combustion engine and improving the efficiency of the emissions control system of the engine, the emissions control system being equipped with a catalyst containing exhaust gas after treatment device, the method comprising:
• lubricating oil composition comprising at least one base oil and at least one overbased low molecular weight zinc dialkyldithiophosphate derived from one or more dithiophosphoric acids represented by the formula
• R 1 and R 2 are independently hydrocarbyl groups, the average total number of carbon atoms in R 1 and R 2 in formula (I) being in the range from 4 to 10, the metal ratio of the overbased low molecular weight zinc dialkyldithiophosphate ratio being at least about 1.15:1 , the lubricating oil composition being characterized by a phosphorus concentration of up to about 0.12% by weight;
• low molecular weight zinc dialkyldithiophosphate may refer to one or more zinc dialkyldithiophosphates derived from one or more dithiophosphoric acids represented by formula (I) wherein the average total number of carbon atoms in R 1 and R 2 for the one or more dithiophosphoric acids represented by formula (I) is up to 10, and in one embodiment in the range from 4 to 10.
• high molecular weight zinc dialkyldithiophosphate may refer to one or more zinc dialkyldithiophosphates derived from one or more dithiophosphoric acids represented by formula (I) wherein the average total number of carbon atoms in R 1 and R 2 in formula (I) is greater than 10.
• overbased is a term of art which is generic to well known classes of metal containing compositions comprising metal salts and/or metal complexes. These compositions may also be referred to as “basic,” “superbased,” “hyperbased,” “high-metal containing salts,” and the like. Overbased metal compositions may be in the form of inert organic liquid solutions characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal (e.g., zinc) and the particular acidic organic compound (e.g., a low molecular weight dialkyldithiophosphoric acid) reacted with the metal.
• the metal e.g., zinc
• the particular acidic organic compound e.g., a low molecular weight dialkyldithiophosphoric acid
• the "neutral" or "normal” metal salt produced will contain one equivalent of zinc for each equivalent of acid.
• an overbased metal composition will contain more than the stoichiometric amount of the metal.
• a low molecular weight dialkyldithiophosphoric acid and/or metal (e.g., zinc) salt thereof may be reacted with a zinc base and the resulting overbased low molecular weight zinc dialkyldithiophosphate may contain an amount of zinc in excess of that necessary to neutralize the acid, for example, about 1.15 times as much zinc as present in the neutral salt or a zinc excess of about 0.15 equivalents.
• the actual stoichiometric excess of zinc may vary considerably, for example, from about 0.10 to about 1.0 equivalents, and in one embodiment from about 0.2 to about 0.5 equivalents.
• metal ratio may be used herein to designate the ratio of the total chemical equivalents of metal (i.e., zinc) in an overbased composition (e.g., overbased low molecular weight zinc dialkyldithiophosphate) to the chemical equivalents of the metal in the corresponding neutral salt.
• metal ratio for a neutral low molecular weight zinc dialkyldithiophosphate is 1 :1
• metal ratio for the overbased low molecular weight zinc dialkyldithiophosphate with a metal excess of 0.15 equivalents discussed above is 1.15:1.
• overbased low molecular weight zinc dialkyldithiophosphate derived from one or more dithiophosphoric acids may refer to an overbased low molecular weight zinc dialkyldithiophosphate which is derived from the dialkyldithiophosphoric acid and/or metal (e.g., zinc) salt of the dialkyldithiophosphoric acid.
• the overbasing of the dithiophosphoric acids or their zinc salts with zinc oxide may be accomplished using catalytic amounts of alkali metal hydroxides such as sodium hydroxide or potassium hydroxide as in US 5,015,402, or catalytic amounts of low molecular weight carboxylic acids such as propionic acid or 2- ethylhexanoic acid as in US 4,263,150 and US4,507,215.
• these catalytic agents are used in as little as 0.01 equivalent or less per 1 phosphorus up to 0.1 or 0.2 or even 0.3 equivalents per 1 phosphorus of the dithiophosphoric acid or salt.
• hydrocarbyl when referring to groups attached to the remainder of a molecule, may refer to groups having a purely hydrocarbon or predominantly hydrocarbon character within the context of this invention. These groups include the following:
• Hetero groups that is, groups which, while predominantly hydrocarbon in character, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Examples include nitrogen, oxygen and sulfur. In general, no more than about three substituents or hetero atoms, and in one embodiment no more than one, may be present for each 10 carbon atoms in the hydrocarbyl group.
• lower as used herein in conjunction with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, may describe such groups which contain a total of up to 7 carbon atoms.
• oil-soluble may refer to a material that is soluble in mineral oil to the extent of at least about 0.5 gram per liter at 25°C.
• TBN may refer to total base number. This is the amount of acid (perchloric or hydrochloric) needed to neutralize all or part of a material's basicity, expressed as milligrams of KOH per gram of sample.
• lean-phosphorus containing exhaust gas may refer to an exhaust gas that is generated in an internal combustion engine lubricated with a lubricating oil composition containing an overbased low molecular weight zinc dialkyldithiophosphate with a metal ratio of at least about 1.08:1 or a Zn/P weight ratio of 1 : 1.15, the exhaust gas having a relatively low concentration of phosphorus when compared to an exhaust gas generated under the same conditions using the same lubricating oil composition containing the same level of phosphorus except that the phosphorus containing compound is a neutral low molecular weight zinc dialkyldithiophosphate or a neutral or overbased high-molecular weight zinc dialkyldithiophosphate.
• substantially absence of copper may refer to the fact that copper may not be intentionally added to the lubricating oil composition and, if present, is present as an impurity.
• concentration of this impurity may be no more than about 10 ppm, and in one embodiment no more than about 5 ppm, and in one embodiment no more than about 2 ppm.
• concentration of copper may be in the range from about 0.1 to about 10 ppm, and in one embodiment in the range from about 0.1 to about 5 ppm, and in one embodiment in the range from about 0.1 to about 2 ppm.
• the lubricating oil composition may comprise of one or more base oils which may be present in a major amount.
• the base oil may be present in an amount greater than about 60% by weight, and in one embodiment greater than about 70% by weight, and in one embodiment greater than about 80% by weight, and in one embodiment greater than about 85% by weight of the lubricating oil composition.
• the lubricating oil composition contains at least one overbased low molecular weight zinc dialkyldithiophosphates.
• the lubricating oil composition may contain an alkali or alkaline earth metal containing detergent, an acylated-nitrogen containing compound which may function as a dispersant, and/or at least one boron-containing compound.
• the lubricating oil composition may contain one or more other additives known in the art.
• the lubricating oil composition may have a viscosity of up to about 16.3 mm 2 /sec at 100 0 C, and in one embodiment in the range from about 5 to about 16.3 mn ⁇ 2 /sec at 100 0 C, and in one embodiment in the range from about 6 to about 13 mm 2 /sec at 1O ⁇ " C.
• the lubricating oil composition may have an SAE Viscosity Grade of OW, OW-20, OW-30, OW-40, OW-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W-40, 15W-50, 2OW or 3OW.
• the lubricating oil composition may be characterized by a sulfur content of up to about 1 % by weight, and in one embodiment up to about 0.5% by weight, and in one embodiment in the range from about 0.01 % to about 1 % by weight, and in one embodiment in the range from about 0.01 % to about 0.5% by weight.
• the lubricating oil composition may be characterized by a phosphorus content of up to about 0.12%, and in one embodiment up to about 0.10%, and in one embodiment up to about 0.08%, and in one embodiment up to about 0.05% by weight, and in one embodiment in the range from about 0.01 to about 0.12%, and in one embodiment in the range from about 0.01 to about 0.10%, and in one embodiment in the range from about 0.01 to about 0.08%, and in one embodiment in the range from about 0.01 to about 0.06%, and in one embodiment in the range form about 0.02 to about 0.12%, and in one embodiment in the range from about 0.02 to about 0.10%, and in one embodiment in the range from about 0.02 to about 0.08%, and in one embodiment in the range from about 0.02 to about 0.06%, and in one embodiment in the range from about 0.03 to about 0.12% by weight, and in one embodiment in the range from about 0.03 to about 0.10% by weight, and in one embodiment in the range from about 0.03 to about 0.08% by weight, and in one embodiment
• the lubricating oil composition may have a boron content in the range up to about 0.2% by weight, and in one embodiment in the range from about 0.01 to about 0.2% by weight, and in one embodiment in the range from about 0.02 to about 0.12% by weight, and in one embodiment in the range from about 0.05 to about 0.1 % by weight.
• the ash content of the lubricating oil composition as determined by the procedures in ASTM D-874-96 may be in the range from about 0.3 to about 1.4% by weight, and in one embodiment in the range from about 0.3 to about 1.2% by weight, and in one embodiment in the range from about 0.3 to about 1.0% by weight.
• the lubricating oil composition may be characterized by a chlorine content of up to about 100 ppm, and in one embodiment up to about 50 ppm, and in one embodiment up to about 10 ppm.
• the Base Oil may be characterized by a chlorine content of up to about 100 ppm, and in one embodiment up to about 50 ppm, and in one embodiment up to about 10 ppm.
• the base oil used in the lubricating oil composition may comprise any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil lnterchangeability Guidelines.
• the five base oil groups are as follows:
• Group I >0.03 and/or ⁇ 90 80 to 120
• PAOs polyalphaolefins
• Groups I, Il and III are mineral oil base stocks.
• the base oil may be a natural oil, synthetic oil or mixture thereof.
• the natural oils include animal oils and vegetable oils (e.g. , castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils derived from coal or shale are also useful.
• Synthetic oils may include hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof.
• the synthetic oils include alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc.; esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, etc.); and esters made from C 5 to Ci 2 monocarboxylic acids and polyols or polyol ethers.
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, etc.
• alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,
• the base oil may comprise a polyalphaolefin (PAO), an oil derived from Fischer-Tropsch synthesized hydrocarbons, or an hydroisomerized Fischer-Tropsch hydrocarbon oil or wax.
• PAO polyalphaolefin
• Group Il or Group III oils, or mixtures thereof may be used.
• mixtures of Group III and Group IV oils may be used.
• Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove may be used as the base oil.
• the overbased low molecular weight zinc dialkyldithiophosphate may be derived from one or more dithiophosphoric acids represented by the formula
• R 1 and R 2 are independently hydrocarbyl groups.
• the average total number of carbon atoms in R 1 and R 2 in Formula I may be up to 10, and in one embodiment in the range from 4 to 10, and in one embodiment in the range from about 5 to 10, and in one embodiment in the range from about 6 to 10, and in one embodiment about 8.
• R 1 and R 2 may be independently hydrocarbyl groups of about 2 to about 8 carbon atoms, and in one embodiment 2 to about 7 carbon atoms, and in one embodiment about 2 to about 6 carbon atoms, and in one embodiment about 2 to about 5 carbon atoms, and in one embodiment about 4 carbon atoms.
• from about 5 to about 70 mole % of the alkyl groups may be C 3 alkyl groups, and from about 70 to about 95 mole % of the groups may comprise one or more alkyl groups of from 2 to about 7 carbon atoms, and in one embodiment from about 2 to about 6 carbon atoms.
• R 1 and R 2 may be independently alkyl groups, alkenyl groups, or mixtures thereof.
• R 1 and R 2 may be derived from one or more primary alcohols, one or more secondary alcohols, or a mixture of at least one primary alcohol and at least one secondary alcohol.
• R 1 and R 2 may include ethyl, isopropyl, butyl, isobutyl, pentyl, 1 ,3 dimethyl-butyl, isooctyl, and the like.
• the low molecular weight dialkyldithiophosphoric acid may be derived from a C 4 alcohol.
• the metal ratio of the overbased low molecular weight zinc dialkyldithiophosphate may be at least about 1.15:1 , and in one embodiment in the range from about 1.15:1 to about 1.5:1 , and in one embodiment in the range from about 1.2:1 to about 1.4:1.
• a metal ratio in the range from 1 :1 to 1.07:1 or a Zn/P wt ratio of up to about 1.12 may be referred to as being neutral or substantially neutral.
• the overbased low molecular zinc dialkyldithiophosphate may be employed in the lubricating oil composition at a concentration sufficient to provide the lubricating oil composition with a phosphorus concentration in the range up to about 0.12% by weight, and in one embodiment in the range from about 0.03 to about 0.12% percent by weight, and in one embodiment in the range from about 0.03% to about 0.10% by weight, and in one embodiment in the range from about 0.03 to about 0.08% by weight, and in one embodiment in the range from about 0.03 to about 0.05% by weight.
• the acylated nitrogen containing compound may contain a substituent comprising at least about 30 aliphatic carbon atoms and may be made by reacting at least one carboxylic acid acylating agent with at least one amino compound.
• the acylating agent may be linked to the amino compound through an imido, amido, amidine or salt linkage.
• the substituent comprising at least about 30 aliphatic carbon atoms may be in either the carboxylic acid acylating agent derived portion of the molecule or in the amino compound derived portion of the molecule.
• substituents may be hydrocarbyl groups made from homo- or interpolymers (e.g., copolymers, terpolymers) of mono- or di-olefins having 2 to about 10 carbon atoms, such as ethylene, propylene, 1 -butene, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc.
• these olefins are 1-monoolefins.
• the substituent may also be derived from the halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers.
• a useful source for the substituent groups may comprise poly(isobutene)s obtained by the polymerization of a C 4 refinery stream having a butene content of about 35 to about 75 weight percent and an isobutene content of about 30 to about 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes may contain predominantly isobutene repeating units.
• the substituent may comprise a polyisobutene group derived from a polyisobutene having a high methylvinylidene isomer content, that is, at least about 50% methylvinylidene, and in one embodiment at least about 70% methylvinylidene.
• These high methylvinylidene polyisobutenes may include those prepared using boron trifluoride catalysts.
• the number average molecular weight of the acylating agent may vary from about 300 up to about 5,000, 10,000 or 20,000.
• the acylating agent may be a hydrocarbyl substituted succinic acid or anhydride containing hydrocarbyl substituent groups and succinic groups wherein the substituent groups are derived from a polyalkene such as polyisobutene.
• the acid or anhydride may be characterized by the presence within its structure of an average of at least about 1 succinic group for each equivalent weight of substituent groups, and in one embodiment from about 1 to about 2.5 succinic groups for each equivalent weight of substituent groups.
• the polyalkene may have number average molecular weight ( M,, ) of at least about 700, and in one embodiment about 700 to about 3000, and in one embodiment about 900 to about 2200.
• the ratio between the weight average molecular weight (Mw) and the (Mn) (that is, Mw/Mn) may range from about 1 to about 10, and in one embodiment about 1.5 to about 5, and in one embodiment about 2.5 to about 5.
• the number of equivalent weights of substituent groups may be deemed to be the number corresponding to the quotient obtained by dividing the IVIn value of the polyalkene from which the substituent is derived into the total weight of the substituent groups present in the substituted succinic acid or anhydride.
• the amino compound may be characterized by the presence within its structure of at least one HN ⁇ group and may be a monoamine or polyamine. Mixtures of two or more amino compounds may be used in the reaction with one or more acylating reagents.
• the amino compound may contain at least one primary amino group (i.e., -NH 2 ).
• the amine may be a polyamine, for example, a polyamine containing at least two -NH- groups, either or both of which are primary or secondary amines.
• the amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic amines. Hydroxy substituted amines, such as alkanol amines (e.g., mono- or diethanol amine), and hydroxy (polyhydrocarbyloxy) anologs of such alkanol amines may be used.
• alkylene polyamines including the polyalkylene polyamines.
• the alkylene polyamines may include those represented by the formula
• R R wherein in Formula (II), n is from 1 to about 14; each R is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted oramine-substituted hydrocarbyl group having up to about 30 atoms, or two R groups on different nitrogen atoms can be joined together to form a U group, with the proviso that at least one R group is a hydrogen atom and U is an alkylene group of about 2 to about 10 carbon atoms. U may be ethylene or propylene. Alkylene polyamines where each R is hydrogen or an amino-substituted hydrocarbyl group with the ethylene polyamines and mixtures of ethylene polyamines are useful.
• n will have an average value of from about 2 to about 10.
• alkylene polyamines include methylene polyamines, ethylene polyamines, propylene polyamines, butylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, amino propylated ethylene polyamines, etc. The higher homologs of such amines and related amino alkyl-substituted piperazines may be included.
• Alkylene polyamines that may be useful may include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, trimethylene diamine, di(trimethylene)triamine, N-(2-amino- ethyl)piperazine, 1 ,4-bis(2-aminoethyl)piperazine, and the like. Higher homologs such as those obtained by condensing two or more of the above-illustrated alkylene amines may be used.
• polyamine bottoms can be characterized as having less than about 2% by weight, and in one embodiment less than about 1 % by weight material boiling below about 200 0 C.
• the acylated nitrogen containing compounds may include amine salts, amides, imides, amidines, amidic acids, amidic salts and imidazolines as well as mixtures thereof.
• one or more acylating reagents and one or more amino compounds may be heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, at temperatures in the range of 8O 0 C up to the decomposition point of any of the reactants or the product but normally at temperatures in the range of about 100 0 C to about 300 0 C, provided 300 0 C does not exceed the decomposition point of any of the reactants or the product.
• acylating agent and the amino compound may be reacted in amounts sufficient to provide from about 0.5 to about 3 moles of amino compound per equivalent of acylating agent.
• the number of equivalents of the acylating agent may vary with the number of carboxy groups present therein. In determining the number of equivalents of the acylating agent, those carboxyl functions which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there is one equivalent of acylating agent for each carboxy group in the acylating agent.
• the use of acylated nitrogen containing compounds with relatively high TBNs in the lubricating oil composition may tend to reduce the volatility of the phosphorus in the overbased low molecular weight zinc dialkyldithiophosphate.
• the acylated nitrogen containing compound may have a TBN (on an oil-free basis) of at least about 2, and in one embodiment in the range from about 2 to about 60, and in one embodiment in the range from about 5 to about 30, and in one embodiment in the range from about 10 to about 20.
• the acylated nitrogen containing compound may be employed in the lubricating oil composition at a concentration in the range from about 1 % to about 20% by weight, and in one embodiment in the range from about 1 % to about 10% percent by weight, and in one embodiment in the range from about 1 % to about 5% by weight.
• the Alkali or Alkaline Earth Metal Containing Detergent may be employed in the lubricating oil composition at a concentration in the range from about 1 % to about 20% by weight, and in one embodiment in the range from about 1 % to about 10% percent by weight, and in one embodiment in the range from about 1 % to about 5% by weight.
• the alkali metal or alkaline earth metal containing detergent may be an alkali or alkaline earth metal salt of an acidic organic compound.
• the acidic organic compound may be an organic sulfur acid, phenol, carboxylic acid or derivative thereof.
• the acidic organic compound may be a salixarate. These salts may be neutral or overbased.
• the former contain an amount of metal cation just sufficient to neutralize the acidic groups present in the salt anion; the latter contain an excess of metal cation and are often termed basic, overbased, hyperbased or superbased salts.
• These salts may have a TBN in the range from about 30 to about 460, and in one embodiment in the range from about 100 to about 400, and in one embodiment in the range from about 200 to about 400, and in one embodiment in the range from about 300 to about 400.
• the organic sulfur acids may be oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acid. Generally they are salts of aliphatic or aromatic sulfonic acids.
• the sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic compounds.
• the carboxylic acids may include aliphatic, cycloaliphatic, and aromatic mono- and polybasic carboxylic acids such as the naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substituted aromatic carboxylic acids.
• the aliphatic acids may contain at least about 8 carbon atoms, and in one embodiment at least about 12 carbon atoms. Usually they have no more than about 400 carbon atoms.
• the cycloaliphatic and aliphatic carboxylic acids may be saturated or unsaturated.
• a useful group of carboxylic acids may be the oil-soluble aromatic carboxylic acids. These acids may be represented by the formula:
• R* is an aliphatic hydrocarbyl group of about 4 to about 400 carbon atoms
• a is an integer of from one to four
• Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms
• each X is independently a sulfur or oxygen atom
• m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least about 8 aliphatic carbon atoms provided by the R* groups for each acid molecule.
• a useful group of carboxylic acids may be the aliphatic-hydrocarbon substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about 8 carbon atoms, and in one embodiment at least about 16 carbon atoms per substituent, and the acids contain one to three substituents per molecule.
• a useful aliphatic-hydrocarbon substituted salicylic acid is Ci 6 -Ci 8 alkyl salicylic acid.
• a group of carboxylic acid derivatives that are useful are the lactones represented by the formula wherein in Formula (IV), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently H, hydrocarbyl groups or hydroxy substituted hydrocarbyl groups of from 1 to about 30 carbon atoms, with the proviso that the total number of carbon atoms must be sufficient to render the lactones oil soluble; R 2 and R 3 can be linked together to form an aliphatic or aromatic ring; and a is a number in the range of zero to 4.
• a useful lactone can be prepared by reacting an alkyl (e.g., dodecyl) phenol with glyoxylic acid at a molar ratio of about 2:1.
• the salixarate may be a substantially linear compound comprising at least one unit of formula (Vl) or formula (VII):
• R 3 is hydrogen or a hydrocarbyl group
• R 2 is hydroxyl or a hydrocarbyl group and j is 0, 1 , or 2
• R 6 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group
• R 4 is hydroxyl and R 5 and R 7 are independently either hydrogen, a hydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R 5 and R 7 are both hydroxyl and R 4 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group
• at least one of R 4 , R 5 , R 6 and R 7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the molecules on average contain at least one of unit (Vl) or (VIII) and at least one of unit (VII) or (I
• -CH 2 - methylene bridge
• -CH 2 OCH 2 - ether bridge
• Salixarate derivatives and methods of their preparation are described in greater detail in U.S. patent number 6,200,936 and PCT Publication WO 01/56968.
• salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
• Mixtures of two or more neutral or basic metal salts of the hereinabove described acidic organic compounds may be used in the lubricating oil compositions.
• the alkali and alkaline earth metals that may be useful may include sodium, potassium, lithium, calcium, magnesium, strontium and barium.
• Sodium, lithium and calcium may be especially useful.
• the use of sodium in the lubricating oil composition may tend to decrease the volatility of the phosphorus used therein significantly. Accordingly, in one embodiment of the invention, the use of sodium as the detergent metal may be particularly useful.
• the alkali or alkaline earth metal containing detergent may be employed in the lubricating oil composition at a concentration in the range from about 0.1 to about 10% by weight, and in one embodiment in the range from about 0.2 to about 5% percent by weight, and in one embodiment in the range from about 0.3% to about 3% by weight, and in one embodiment in the range from about 0.5 to about 2% by weight.
• the boron-containing compound may be is a compound represented by one or more of the formulae
• each R may be independently an organic group and any two adjacent R groups may together form a cyclic group. Mixtures of two or more of the foregoing may be used.
• each R may be independently a hydrocarbyl group.
• the total number of carbon atoms in the R groups in each formula may be sufficient to render the compound soluble in the base oil.
• the total number of carbon atoms in the R groups may be at least about 8, and in one embodiment at least about 10, and in one embodiment at least about 12. There may be no limit to the total number of carbon atoms in the R groups that is required, but a practical upper limit may be about 400 or about 500 carbon atoms.
• each R group may be independently a hydrocarbyl group of 1 to about 100 carbon atoms, and in one embodiment 1 to about 50 carbon atoms, and in one embodiment 1 to about 30 carbon atoms, and in one embodiment 1 to about 10 carbon atoms, with the proviso that the total number of carbons in the R group may be at least about 8.
• Each R group may be the same as the other, although they may be different.
• R groups may include isopropyl, n-butyl, isobutyl, amyl, 1 ,3 dimethyl-butyl, 2-ethyl-1-hexyl, isooctyl, decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and the like.
• the boron-containing compound may be a compound represented by the formula ( x ⁇ v )
• R 1 , R 2 , R 3 and R 4 are independently hydrocarbyl groups of 1 to about 12 carbon atoms; and R 5 and R 6 are independently alkylene groups of 1 to about 6 carbon atoms, and in one embodiment about 2 to about 4 carbon atoms, and in one embodiment about 2 or about 3 carbon atoms.
• R 1 and R 2 may independently contain 1 to about 6 carbon atoms, and in one embodiment each may be a t-butyl group.
• R 3 and R 4 are independently hydrocarbyl groups of about 2 to about 12 carbon atoms, and in one embodiment about 8 to about 10 carbon atoms.
• R 5 and R 6 are independently -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
• the boron-containing compound may be a compound represented by the formula:
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen or hydrocarbyl groups.
• Each of the hydrocarbyl groups may contain from 1 to about 12 carbon atoms, and in one embodiment 1 to about 4 carbon atoms.
• An example is 2,2-oxy-bis-(4,4,6-t ⁇ methyl-1 ,3,2-dioxaborinane).
• a useful boron-containing compound may be available from Crompton Corporation under the trade designation LA-2607. This material may be identified as a phenolic borate having the structure represented by Formula (XIV) wherein R 1 and R 2 are each t-butyl, R 3 and R 4 are hydrocarbyl groups of 2 to about 12 carbon atoms, R 5 is -CH 2 CH 2 -, and R 6 is -CH 2 CH 2 CH 2 -.
• the boron-containing compound may be a compound represented by the formula B(OC 5 H 11 ) or B(OC 4 Hg) 3 .
• a useful boron-containing compound may be available from Mobil under the trade designation MCP-1286; this material may be identified as a borated ester.
• the boron-containing compound may be employed in the lubricating oil composition at a sufficient concentration to provide the lubricating oil composition with a boron concentration in the range up to about 0.2% by weight, and in one embodiment in the range from about 0.01% to about 0.2% by weight, and in one embodiment in the range from about 0.02% to about 0.12% by weight, and in one embodiment in the range from about 0.05% to about 0.1% by weight.
• These compounds may be added directly to the lubricating oil composition. In one embodiment, however, they may be diluted with a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil (e.g., ester of dicarboxylic acid), naptha, alkylated (e.g.
• the lubricating oil composition may also contain other lubricant additives. These may include, for example, corrosion-inhibiting agents, antioxidants, viscosity modifiers, dispersant viscosity index modifiers, pour point depressants, friction modifiers, antiwear agents other than those discussed above, EP agents other than those discussed above, dispersants other than those discussed above, detergents other than those discussed above, fluidity modifiers, copper passivators, anti-foam agents, etc. Each of the foregoing additives, when used, may be used at a functionally effective amount to impart the desired properties to the lubricant.
• the concentration of each of these additives when used, may be in the range from about 0.001 % to about 20% by weight, and in one embodiment in the range from about 0.01 % to about 10% by weight based on the total weight of the lubricating oil composition.
• the foregoing lubricating oil additives may be added directly to the base oil to form the lubricating oil composition.
• one or more of the additives may be diluted with a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil, naphtha, alkylated (e.g., C 10 -Ci 3 alkyl) benzene, toluene or xylene to form an additive concentrate.
• a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil, naphtha, alkylated (e.g., C 10 -Ci 3 alkyl) benzene, toluene or xylene to form an additive concentrate.
• These concentrates may contain from about 1 % to about 99% by weight, and in one embodiment from about 10% to 90% by weight of such diluent.
• the concentrates may be added to the base oil to form the lubricating oil composition.
• the disclosed method may provide for lubricating an internal combustion engine and improving the efficiency of the emissions control system of the engine wherein the emissions control system is equipped with a catalyst-containing exhaust gas after treatment device used with the engine.
• the lubricating oil composition may generate a lean-phosphorus containing exhaust gas during operation of the engine.
• the lean-phosphorus containing exhaust gas may be advanced to the exhaust gas after treatment device. In the exhaust gas after treatment device the lean-phosphorus containing exhaust gas may contact the catalyst.
• the phosphorus in the lean-phosphorus containing exhaust gas may contaminate the catalyst and thereby reduce its efficiency.
• the level of phosphorus in the lean- phosphorus containing exhaust gas may be at a reduced level, the amount of contamination of the catalyst may be reduced.
• the generation of a lean-phosphorus containing exhaust gas may be dependent on the use of the lubricating oil composition.
• the use of the overbased low molecular weight dialkyldithiophosphate in the lubricating oil composition may provide for low-phosphorus volatility when the lubricating oil composition is used to lubricate an internal combustion engine.
• the lubricating oil composition may also contain one or more alkali or alkaline earth metal containing detergents, one or more acylated-nitrogen containing compounds, and/or one or more boron containing compounds.
• the combination of these additives with the overbased low molecular weight dialkyldithiophosphate may contribute to reducing the volatility of the overbased low molecular weight zinc dialkyldithiophosphate.
• Additional optional nitrogen-containing compounds e.g., antioxidants
• This reduction in phosphorus volatility may provide for the generation of a lean-phosphorus containing exhaust gas.
• the weight ratio of detergent metal to phosphorus in the lubricating oil composition at the time the lubricating oil composition may be added to the engine may be in the range from about 0.5:1 to about 10:1 , and in one embodiment in the range from about 2: 1 to about 4:1 , and in one embodiment in the range from about 2.5:1 to about 3:1.
• the weight ratio of basic (titratable) nitrogen to phosphorus in the lubricating oil composition at the time the lubricating oil composition may be added to the engine may be in the range from about 0.3:1 to about 4:1 , and in one embodiment about 0.5: 1 to about 2: 1 , and in one embodiment in the range from about 1 :1 to about 1.5:1.
• the amount of phosphorus in the exhaust gas during the operation of the engine may be indirectly proportional to the amount of phosphorus retained in the lubricating oil composition in the crankcase.
• the amount of phosphorus retained in the crankcase may be calculated from the following formula: (%Wt P d rain)(% Wt M new )
• %Wt Pnew (%Wt M dra in) wherein: % wt P dra i n is the percent by weight of phosphorus in the lubricating oil composition in the crankcase at the end of a drain interval; % wt M new is the percent by weight of detergent metal in the lubricating oil composition in the crankcase at the beginning of the drain interval; % wt P new is the percent by weight of phosphorus in the lubricating oil composition in the crankcase at the beginning of the drain interval; and % wt M d r a i n is the percent by weight of detergent metal in the lubricating oil composition at the end of the drain interval.
• the amount of phosphorus retained in the crankcase oil of the engine after a 12000 kilometer (7500 mile) drain cycle may be at least about 80% by weight, and in one embodiment at least about 84% by weight, and in one embodiment at least about 88% by weight, and in one embodiment at least about 92% by weight, and in one embodiment at least about 95% by weight, and in one embodiment at least about 98% by weight.
• the amount of phosphorus lost from the crankcase oil with the exhaust gas over a 7500 mile (12000 kilometer) drain cycle may be about 20% by weight or less, and in one embodiment about 16% by weight or less, and in one embodiment about 12% by weight or less, and in one embodiment about 8% by weight or less, and in one embodiment about 5% by weight or less, and in one embodiment about 2% by weight or less.
• Copper in the lubricating oil composition may increase the volatility of the phosphorus used therein. Accordingly, at the time of its addition to the engine, the lubricating oil composition may be characterized by the substantial absence of copper.
• the internal combustion engine may be any internal combustion engine that is equipped with exhaust gas after treatment device that utilizes a catalyst. These may include engines that employ a closed crankcase system and positive crankcase ventilation.
• the internal combustion engine may be a spark-ignited or a compression-ignited engine. These engines may include automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. These may include on- and off-highway engines.
• the compression-ignited engines may include those for both mobile and stationary power plants.
• the compression-ignited engines may include those used in urban buses, as well as all classes of trucks.
• the compression-ignited engines may be of the two-stroke per cycle or four-stroke per cycle type.
• the compression-ignited engines may include heavy duty diesel engines.
• the exhaust gas after treatment device may be referred to as a catalytic converter and may be of any conventional design.
• the exhaust gas after treatment device may comprise flow-through passages of ceramic or metal coated with a washcoat comprising zeolite, AI 2 O 3 , SiO 2 , TiO 2 , CeO 2 , ZrO 2 , V 2 O 5 , La 2 O 3 , or mixtures of two or more thereof.
• the washcoat may support a catalyst comprising Pt, Pd, Rh, Ir, Ru 1 V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Ce, Ga, or a mixture of two or more thereof. Examples
• Engine tests are conducted using a 1997 GM 5.2L V-8 DOHC equipped with a roller-follower valve train.
• the test duration is 25 hours.
• the engine conditions are: 2640 rpm; 29.8 kilowatt load (calculated); 210 0 F (98.9 0 C) oil temperature; and 180 0 F (82.2°C) coolant temperature.
• the exhaust gas is analyzed for volatile phosphorus compounds. Elemental analysis (by ICP) and phosphorus NMR are used.
• the lubricating oil compositions used in the tests are provided in Table I. In Table I, unless otherwise indicated, all numerical values are in parts by weight.
• Examples 1 and 2 are almost as good as Examples C-2 and C- 3 in terms of blow-by phosphorus, in spite of their lower molecular weight substituents.
• the lower molecular weight substituents are believed to provide improved wear protection as compared with the longer chain materials of Examples C-2 and C-3.

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• 2007
  • 2007-07-13 EP EP07812891A patent/EP2041247A2/de not_active Withdrawn
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