Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Heterocyclic ring compound; a heterocyclic ring is one...
Reexamination Certificate
2000-11-28
2003-03-04
McAvoy, Ellen M. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Heterocyclic ring compound; a heterocyclic ring is one...
C508S364000
Reexamination Certificate
active
06528461
ABSTRACT:
TECHNICAL FIELD
This invention relates to engine oil lubricants and engine oil lubricant concentrates having enhanced frictional properties and improved fuel economy, methods for their preparation, and their use. The lubricating oil compositions of this invention are particularly useful as crankcase lubricants.
BACKGROUND OF THE INVENTION
An automotive crankcase is subjected to well known extremes of heat and friction which cause engine oil breakdown, as well as contribute to the presence of contaminants including dirt, soot, water and other particulate matter.
This environment results in the oil suffering oxidation that is catalyzed by the presence of impurities in the oil such as iron compounds, and the oxidation is enhanced by the elevated temperatures endured during engine use.
Various engine oil additives are known for improving the internal operating condition of an engine, including anti-wear agents, antioxidants, friction modifiers, detergents, and dispersants. Each may improve the oil through controlling any of various degradations suffered during use.
The additives may be added to the fuel composition, the engine oil, or other lubricants and greases as appropriate, be they synthetic or natural.
Dispersants of various forms are known. These are primarily additives for lubricating oils, which function at low operating temperatures to prevent or retard the formation of sludge, and also to solubilize the sludges which are formed. In structure, most dispersants have a polar and nonpolar portion. The nonpolar portion is frequently a polybutene, and the polar portion contains amino groups.
The industry trend is to provide ashless dispersants, i.e., without metal.
Succinimide dispersants are well known, they are typically based on polybutene (900-3000 Mn) adducts of maleic anhydride reacted with various polyamines, e.g. tetraethylene pentamine or triethylene tetramine. Bis-succinimides are generally preferred over monosuccinimides, even though product viscosities are higher. Succinate esters, based on polybutene adducts that are esterified with polyols, e.g. pentaerythritol, are also known.
Mannich base products consisting of condensation products from polybutene alkylphenol, formaldehyde, and polyamines are also known.
Alkenyl-substituted succinic anhydrides derived dispersants are well known. Such alkenyl-substituted succinic anhydrides are typically prepared by a thermal process (see, e.g., U.S. Pat. No. 3,361,673), or a mixed thermal/chlorination process (see, e.g., U.S. Pat. No. 3,172,892). The polyisobutenyl succinic anhydrides (“PIBSA”) include monomeric adducts (see, e.g., U.S. Pat. Nos. 3,219,666; 3,381,022) and products adducted with at least 1.3 succinic groups per polyalkenyl-derived substituent (see, e.g., U.S. Pat. No. 4,234,435 to Meinhardt).
PIBSA serves as a ubiquitous precursor to several crankcase ashless dispersants, including succinimides, succinates, succinate esters amides, and triazoles (U.S. Pat. Nos. 3,272,746; 4,234,435; 3,219,666; 4,873,009; 4,908,145; and 5,080,815). In the formation of succinimides, the PIBSA is reacted with a polyamine to form a structurally complex mixture that may contain imide, amide, and imidazoline and diamide groups.
The above-mentioned Mannich base dispersants represent another known class of crankcase dispersants (e.g. HiTEC® 7049 dispersant, available from Ethyl Corporation, of Richmond, Va.). These compounds are typically produced by reacting alkyl-substituted phenols with aldehydes and amines, such as is described in U.S. Pat. Nos. 3,539,633; 3,697,574; 3,704,308; 3,736,535; 3,736,357; 4,334,085; and 5,433,875.
Also known are functionalized olefin copolymers and their use as additives in fuel and lubricating oil compositions, as described in U.S. Pat. No. 6,107,258, which describes a cross linked low molecular weight ethylene-propylene succinic anhydride dispersant. The functionalized olefin copolymers disclosed therein include an olefin copolymer on which has been grafted an ethylenically unsaturated carboxylic acid, or derivative thereof, to form an acylated olefin copolymer containing reactive carboxylic functionality. The acylated olefin copolymer is then reacted with a coupling compound, which contains more than one amine, thiol and/or hydroxy functionality capable of reacting with the carboxylic functionality of preferably more than one acylated olefin copolymer.
Additionally, the acylated olefin copolymers, either before or after reaction with the coupling compound, are reacted with a performance enhancing compound or compounds, i.e., compounds containing only one functional group capable of reacting with the carboxylic functionality of the acylated olefin copolymer, in order to obtain further benefits such as improved antioxidancy, antiwear and additional dispersancy properties.
Molybdenum is a well-known wear inhibitor (friction modifier), and available commercially in many forms.
Molybdenum carboxylate salts are known to increase fuel economy. Various organo molybdenum compounds are available for inclusion in a lubricating oil, including molybdenum ditridecyldithiocarbonate, and others.
U.S. Pat. No. 3,144,712 discloses oil-soluble molybdenum additives useful in lubricating oils such as molybdates of organic nitrogen bases.
Molybdenum dialkyldithiocarbamates are described in U.S. Pat. Nos. 4,098,705; 4,846,983; 5,916,851; 3,356,702; 3,509,051; and 4,098,705.
U.S. Pat. No. 4,176,074 to Coupland discloses molybdenum complexes of ashless oxazoline dispersants as friction reducing antiwear additives for lubricating oils.
U.S. Pat. No. 4,266,945 to Karn discloses molybdenum containing compositions prepared by reacting an acid or salt of molybdenum, a phenol or reaction product of a phenol and at least one lower aldehyde, and an amine, condensation product of an amine, and salts of an amine or condensation product of an amine.
U.S. Pat. No. 4,324,672 to Levine discloses molybdenum derivatives of high molecular weight alkenylsuccinimides.
U.S. Pat. No. 5,650,380 to Fletcher discloses a lubricating composition including a base oil of mineral or synthetic in origin in combination with molybdenum disulfide, zinc naphthenate, and one or more metal dithiophosphates, with optionally one or more metal dithiocarbamates.
U.S. Pat. No. 5,650,381 to Gatto et al. discloses a lubricating oil composition comprising a molybdenum compound which is substantially free of active sulfur and a secondary diarylamine. This combination is said to provide improved oxidation control and friction modifier performance to the lubricating oil.
U.S. Pat. No. 5,736,491 to Patel discloses improving fuel economy characteristics of a lubricant by friction reduction by mixing the lubricant with a C2 to C12 aliphatic carboxylate salt of molybdenum and a zinc dialkyldithiophosphate or zinc dialkyldithiocarbamate.
U.S. Pat. No. 5,744,430 to Inoue et al. discloses, with certain limiting conditions, a base oil with an alkaline earth metal salicylate detergent, a zinc dialkyldithiophosphate, a succinimide ashless dispersant containing a polybutenyl group, a phenol ashless antioxidant, a molybdenum dithiocarbamate friction modifier, and a viscosity index improver.
Molybdenum containing additives are known to deliver a variety of beneficial properties to lubricants. Examples of lubricants that benefit from the addition of molybdenum include passenger car motor oils, natural gas engine oils, heavy duty diesel oils, and railroad oils. Over the years, when used properly, molybdenum has been shown to deliver improved anti-wear protection, improved oxidation control, improved deposit control, and improved friction modification for fuel economy.
The prior art is replete with examples showing the use of molybdenum as antioxidants, deposit control additives, anti-wear additives, and friction modifiers. Some of these include U.S. Pat. Nos. 4,360,438; 4,501,678; 4,529,526; 4,692,256; 4,705,641; 4,812,246; 4,832,867; 5,458,807; 5,605,880; 5,650,381; 5,658,862; 5,665,684; 5,688,748; 5,696,065; 5,736,491; 5,763,369; 5,786,307; 5,807,813; 5,814,587; 5,837,657; 5,840,672
Devlin Mark T.
Esche Carl K.
Mike Carl A.
Bank of America, N.A.
McAvoy Ellen M.
LandOfFree
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