Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Organic -co- compound
Reexamination Certificate
1994-10-17
2001-10-30
Johnson, Jerry D. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Organic -co- compound
Reexamination Certificate
active
06310011
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to certain overbased metal salts useful as additives for lubricants based on oils of lubricating viscosity. More particularly, it relates to metal carboxylates of alkylene bis-phenol alkanoic acids and related hydroxy carboxylates. These materials, as well as corresponding neutral salts and certain lactones, are particularly useful as additives for marine diesel lubricants.
The field of lubricant technology is characterized by a never-ending search for improved lubricants and additives. Additives, essential for satisfactory performance of lubricants for all manner of modern engines, serve many roles, including those of providing detergency, antioxidant properties, and suspension of contaminants. The latter function is particularly critical in engines which burn fuel containing asphaltene components, since asphaltenes are often found to contaminate the lubricating oil through blow-by past piston rings. The additives of the present invention, besides their general utility as detergents and antioxidants in many applications such as general diesel applications, are particularly useful in marine diesel engines. Marine diesel engines are typically two- or four-stroke compression ignited engines commonly used in ships for main propulsion or auxiliary power generation applications, or in stationary land-based power generation applications. Marine diesel engines are commonly designed to run on a variety of diesel fuels from good quality light distillate fuel with low sulfur and asphaltene content to poorer quality intermediate or heavy fuels like “Bunker C” or residual fuel oil with generally higher sulfur and asphaltene content. Four stroke engines designs have crankcase oil systems which can become contaminated with diesel fuel either through blow-by or fuel leakage directly into the lubricating oil. Hence the present lubricants are particularly useful in providing asphaltene suspension in lubricants which are employed in the lubrication of such engines.
PCT Publication WO 93/21143, Blystone et al., published Oct. 28, 1993 discloses metal carboxylates of alkylene bis-phenol alkanoic acids useful as additives for fuels and lubricants.
U.S. Pat. No. 5,281,346, Adams et al., Jan. 25, 1994, discloses lubricants for two-cycle engines comprising a major amount of at least one oil of lubricating viscosity and a minor amount of certain compounds of the general formula A
Y−
M
y+
. A is an anion containing group with a carboxylic aromatic structure.
U.S. Pat. No. 2,933,520 to Bader relates to compounds represented by the formula
in which R
1
may be hydrocarbon, halogen, R
2
is hydrocarbon, e.g., alkylene other than methylene and containing at least two carbon atoms and containing up to 10, 12 or even more carbon atoms, Ar groups are aromatic rings, unsubstituted or substituted with alkyl, halogen, nitro, sulfo and others, the nature of each of these groups affecting properties such as boiling point, solubility, toxicity, and bactericidal, fungicidal, insecticidal and like properties.
U.S. Pat. No. 3,038,935 to Gerber et al. teaches the preparation of compounds of the formula
wherein each R is an aliphatic, cycloaliphatic or aromatic radical, Me is Na, K or Li, by reacting alkali metal salts of hindered phenols with dichloroacetic acid. Products are said to be useful for production of rubber auxiliaries, mineral oil additives and stabilizers for plastics.
U.S. Pat. No. 3,133,944 to Christensen teaches heavy metal salts represented by
wherein the R
1
is alkyl of 1-4 carbons, R
2
is alkylene of 2-6 carbons and Ar is an aromatic group which may be substituted with one or more methyl groups and others. The salts are said to be adapted to retard or prevent the growth of biological organisms, particularly molds and mildews.
U.S. Pat. No. 3,471,537 to Berke et al. teaches diphenolic compounds of the formulas
wherein X and X
1
are halogen or hydrogen, salts and derivatives as useful for germicides and antiseptics and disinfectants.
U.S. Pat. No. 4,828,733 to Farng et al. relates to copper salts of hindered phenol carboxylic acids.
U.S. Pat. No. 4,627,928, Karn, Dec. 9, 1986, discloses basic magnesium salts of substituted aromatic hydroxy carboxylic acids (e.g. salicylic acids) which can be used in lubricating oils.
A wide variety of metal-containing compounds have been employed, with varying degrees of success as lubricating oil additives. Illustrative are detergents of the ash-containing type. These are well-known in the art and include Newtonian and non-Newtonian neutral and overbased salts of alkali, alkaline earth and transition metals with, for example, sulfonic acids, carboxylic acids, salicylic acids, phosphorus-containing acids, phenols and the like. Among the many publications which disclose overbased metal salts and their method of preparation and use is U.S. Pat. No. 3,429,231, McMillen, Jan. 27, 1970 and U.S. Pat. No. 4,627,928, Karn, Dec. 9, 1986.
SUMMARY OF THE INVENTION
The present invention provides an overbased metal salt of an acidic material selected from the group consisting of (a) hydrocarbyl-substituted carboxyalkylene-linked phenols, (b) dihydrocarbyl esters of alkylene dicarboxylic acids, the alkylene group being substituted with a hydroxy group and an additional carboxylic acid group, and (c) alkylene-linked polyaromatic molecules, the aromatic moieties whereof comprise at least one hydrocarbyl-substituted phenol and at least one carboxy phenol; the hydrocarbyl group or groups of said acidic material being of sufficient length to provide oil solubility to the salt.
The invention further provides lubricants containing the above additives a method for lubricating engines by use of such a lubricant, and, in particular, a method for lubricating an internal combustion engine which burns fuel containing asphaltene components, comprising supplying to the engine a lubricant comprising:
(a) an oil of lubricating viscosity, and
(b) a material selected from the group consisting of (i) metal salts of hydrocarbyl-substituted carboxyalkylene-linked phenols, (ii)metal salts of dihydrocarbyl esters of alkylene dicarboxylic acids, the alkylene group being substituted with a hydroxy group and an additional carboxylic acid group, (iii) metal salts of alkylene-linked polyaromatic molecules, the aromatic moieties whereof comprise at least one hydrocarbyl-substituted phenol and at least one carboxy phenol, and (iv) lactones of hydrocarbyl-substituted carboxyalkylene-linked phenols.
The lubrication process is generally made complete by operating the engine.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to overbased metal salts of a variety of types, and their use of lubricants. Overbased materials are single phase, homogeneous, generally Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
The amount of excess metal is commonly expressed in terms of metal ratio. The term “metal ratio” is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound. A neutral metal salt has a metal ratio of one. A salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The basic salts of the present invention have a metal ratio of at least 1.3, preferably at least 1.5, preferably up to 40, more preferably 20, and even more preferably 10. A preferred metal ratio is 2-6.
The basicity of the overbased materials of the present invention generally is expressed in terms of a total base number. A total base number is the amount of acid (perchloric or hydrochloric) needed to neutralize all of the overbased material's basicity. The amount of acid is expressed as potassium hydroxide equivalents. Total base number is determined by titration of one gram of overbased material with 0.1 Normal hydrochloric acid solution using bromophenol blue as an indicator. The overbased mat
Adams Paul E.
Karn Jack L.
King Laurence E.
Kocsis Jody A.
Notaro Vincent A.
Esposito Michael F.
Johnson Jerry D.
Shold David M.
The Lubrizol Corporation
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