Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-01-21
2002-03-26
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S010000, C556S024000, C556S057000, C252S363500
Reexamination Certificate
active
06362355
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to molybdated dispersants suitable for use as lubricant additives, and a method for their preparation.
Current engine lubrication technology requires ever-improving performance of the lubricant in order to assure adequate lubrication of demanding engines. It is known that the presence of molybdenum compounds can in many instances provide improvements in anti-wear performance and, in particular, friction reduction and, as a consequence, fuel economy. However, many molybdenum compounds are expensive or difficult to provide in a suitably oil-soluble form.
Canadian Patent 623,155, Jul. 4, 1961, discloses lubricant additives containing molybdenum compounds. Phosphomolybdic acid is reacted with an organic nitrogen base and reduced by reaction with an organic compound to a form in which at least a part of the Mo is tetravalent. The resulting product has improved solubility. Suitable nitrogen bases include (in the claims) hydrocarbon acyl amines. All known organic nitrogen bases that are soluble in or at least compatible with liquid lubricants are said to be suitable for use in neutralizing and reducing phosphomolybdic acid and for neutralizing and enhancing the thermal stability of an acidic reaction product of phosphomolybdic acid with a non-basic reducing agent. The final reaction products are said to be useful as lubricant additives.
U.S. Pat. No. 5,319,119, Kaneshima et al., Jun. 7, 1994, discloses oleophilic molybdenum compounds comprising an aliphatic amine group and a heteropolyanion group. The oleophilic molybdenum compound is a catalyst precursor capable of being changed to a catalyst having excellent catalytic activity. The catalyst can be prepared by reacting an aliphatic amine with a heteropolyacid in a hydrocarbon oil. Lubricating oil is disclosed as an illustrative hydrocarbon oil.
The present invention, therefore, solves the problem of improving lubricant performance, particularly in terms of friction reduction, in an economical manner by providing oil-soluble molybdenum compositions which can be prepared by a convenient route.
SUMMARY OF THE INVENTION
The present invention provides a molybdated dispersant composition prepared by reacting phosphoric acid or silicic acid, MoO
3
, and an amine-containing dispersant. Otherwise stated, it provides a molybdated dispersant composition represented by the formula:
(R
1
—NR
2
R
3
H
+
)
m−n
X
n
(MoHPA)
m−
wherein R
1
—NR
2
R
3
represents the amine-containing dispersant, R
1
is a group providing dispersant properties to said dispersant composition, each of R
2
and R
3
is independently hydrogen, a hydrocarbyl group, or an additional R
1
group; X is hydrogen, a monovalent metal ion, a single valence of a polyvalent metal ion, an ammonium ion, or an amine cation, m is 3 or 4, n is 0 to 2.5 when m is 3 and 0 to 3.5 when m is 4, and (MoHPA)
m−
is a molybdenum heteropolyacid anion of charge m.
The invention similarly provides a process for preparing a molybdated composition comprising reacting phosphoric acid or silicic acid with MoO
3
and with an amine, such as an amine-containing dispersant.
The invention further provides a lubricant composition comprising a major amount of an oil of lubricating viscosity and such a molybdated dispersant, or a concentrate thereof.
DETAILED DESCRIPTION OF THE INVENTION
Various preferred features and embodiments will be described below by way of non-limiting illustration.
The present invention provides a molybdated dispersant composition. It is believed that the molybdated dispersant has, at least in part, a composition or structure which can be reasonably represented by the formula:
(R
1
—NR
2
R
3
H
+
)
m−n
X
n
(MoHPA)
m−
In this formula, R
1
—NR
2
R
3
represents an amine-containing dispersant in which R
1
is a group providing dispersant properties to said dispersant composition. That is, R
1
, or a portion of R
1
, is a group which provides sufficient solubility properties to the molybdenum-containing composition set forth above so that it can be readily dispersed or dissolved in oil. Thus, the entire moiety R
1
—NR
2
R
3
can be considered to be a dispersant, and it generally comprises a relatively less polar R
1
group, together with a generally more polar NR
2
R
3
portion, both groups together serving to provide the dispersant properties. The more polar portion, or head, serves to interact with polar substances, which ordinarily would be dirt or contaminant particles; but for the purposes of the present invention, it interacts with the molybdenum heteropolyacid. The less polar portion provides oil solubility to permit the compound or complex to be dissolved or dispersed in oil. It is possible that an R1 group also contains additional amine groups, which may be considered to be a part of the polar “head” of the dispersant, provided that at least a portion of an R1 group is a suitably non-polar moiety. Indeed, some of the additional amine groups which may be present in R1 may form additional salt structures or otherwise interact with additional molybdenum heteropolyacids to form more complicated structures such as:
(MoHPA)
m−
X
n
(+HR
2
R
3
N—R
4
—NR
2
R
3
H
+
)X
n
(MoHPA)
m−
(ignoring for the purpose of illustration the stoichiometry of the structure) where R
4
is a linking group such as a straight chain or branched alkylene group, and the other terms are as described below.
In the formula (R
1
—NR
2
R
3
H
+
)
m−n
X
n
(MoHPA)
m−
, each of R
2
and R
3
is independently hydrogen, a hydrocarbyl group, or an additional R1 group as defined above. That is, R
2
or R
3
may also provide dispersant properties to the complex.
Amine-containing dispersants in general can include acylated amines, amine-containing carboxylic esters, Mannich reaction products, hydrocarbyl substituted amines, and mixtures thereof.
Acylated amine dispersants include reaction products of one or more carboxylic acylating agent and one or more amine. The carboxylic acylating agents include C8-30 fatty acids, C14-20 isoaliphatic acids, and hydrocarbyl substituted carboxylic acylating agents. Dimer acids are described in U.S. Pat. Nos. 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468, 3,157,681, and 3,256,304. The addition carboxylic acylating agents are addition (4+2 and 2+2) products of an unsaturated fatty acid with one or more unsaturated carboxylic reagents. These acids are taught in U.S. Pat. No. No. 2,444,328. In another embodiment, the carboxylic acylating agent is a hydrocarbyl substituted carboxylic acylating agent. The hydrocarbyl substituted carboxylic acylating agents are prepared by a reaction of one or more of olefins or polyalkenes with one or more of unsaturated carboxylic agents, such as itaconic, citraconic, or maleic acylating agents, typically at a temperature of 160°, or 185° C. up to 240° C., or to 210° C. Maleic acylating agents are the preferred unsaturated acylating agent. The procedures for preparing the acylating agents are. well known to those skilled in the art and have been described for example in U.S. Pat. No. 3,412,111; and Ben et al., “The Ene Reaction of Maleic Anhydride With Alkenes”, J. C. S. Perkin II (1977), pages 535-537. A preferred acylating agent is a hydrocarbyl-substituted succinic anhydride or the reactive equivalent thereof (e.g., an acid, acid halide, half ester). The hydrocarbyl substituent thereon is, in a preferred embodiment, a polymer of isobutylene having a number average molecular weight of 500 to 5000, preferably 900 to 3500.
The amines which react with the acylating agents may be known amines, and in the present instance a polyamine, such that at least one amine functionality can remain unacylated and available for reaction to form the molybdated dispersant of the present invention. Polyamines include aliphatic, cycloaliphatic, heterocyclic or aromatic polyamines and alkylene polyamines, condensed polyamines, hydroxy containing polyamines, arylpolyamines, and heterocyclic polyamines.
Alkylene polyamines ar
Steckel Thomas F.
Zhu Ping Y.
Esposito Michael F.
Nazario-Gonzalez Porfirio
Shold David M.
The Lubrizol Corporation
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