U.S. patent application number 13/398972 was filed with the patent office on 2012-06-14 for lubricating oil composition.
This patent application is currently assigned to CHEVRON U.S.A. INC.. Invention is credited to ALEXANDER B. BOFFA, RICHARD E. CHERPECK, WILLIAM M. KLEISER, JAMES A. MCGEEHAN, KENNETH D. NELSON, STEPHEN D. STULTS, WIM VAN DAM.
Application Number | 20120145114 13/398972 |
Document ID | / |
Family ID | 42241236 |
Filed Date | 2012-06-14 |
United States Patent
Application |
20120145114 |
Kind Code |
A1 |
NELSON; KENNETH D. ; et
al. |
June 14, 2012 |
LUBRICATING OIL COMPOSITION
Abstract
A lubricating oil composition having a sulfur content of up to
about 0.4 wt. % and a sulfated ash content of up to about 0.5 wt. %
as determined by ASTM D874 is disclosed which comprises (a) a major
amount of an oil of lubricating viscosity; (b) at least one
oil-soluble or dispersed oil-stable boron-containing compound
having no more than about 400 ppm of boron; and (c) at least one
oil-soluble or dispersed oil-stable molybdenum-containing compound
having, at least about 1100 ppm of molybdenum, based upon the total
mass of the composition; wherein the lubricating oil composition
has a ratio of sulfur to molybdenum of less than or equal to about
4:1.
Inventors: |
NELSON; KENNETH D.; (NAPA,
CA) ; BOFFA; ALEXANDER B.; (OAKLAND, CA) ;
KLEISER; WILLIAM M.; (LAFAYETTE, CA) ; STULTS;
STEPHEN D.; (BENICIA, CA) ; MCGEEHAN; JAMES A.;
(SAN RAFAEL, CA) ; VAN DAM; WIM; (BERGSCHENHOEK,
NL) ; CHERPECK; RICHARD E.; (COTATI, CA) |
Assignee: |
CHEVRON U.S.A. INC.
SAN RAMON
CA
CHEVRON ORONITE COMPANY LLC
SAN RAMON
CA
|
Family ID: |
42241236 |
Appl. No.: |
13/398972 |
Filed: |
February 17, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12316894 |
Dec 17, 2008 |
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13398972 |
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Current U.S.
Class: |
123/196R ;
508/156; 508/186 |
Current CPC
Class: |
C10M 2207/042 20130101;
C10M 2227/09 20130101; C10M 2227/061 20130101; C10M 2219/102
20130101; C10M 2215/28 20130101; C10M 2201/087 20130101; C10M
2219/046 20130101; C10N 2030/43 20200501; C10M 2227/062 20130101;
C10N 2040/252 20200501; C10N 2040/25 20130101; C10M 2219/044
20130101; C10M 2215/064 20130101; C10M 2203/1006 20130101; C10N
2060/14 20130101; C10M 2219/068 20130101; C10N 2040/255 20200501;
C10N 2030/45 20200501; C10M 141/12 20130101; C10M 2215/08 20130101;
C10M 2207/026 20130101; C10M 163/00 20130101; C10N 2030/42
20200501; C10M 2219/066 20130101; C10M 2207/042 20130101; C10N
2060/14 20130101; C10M 2215/08 20130101; C10N 2060/14 20130101;
C10M 2215/28 20130101; C10N 2060/14 20130101; C10M 2219/044
20130101; C10N 2060/14 20130101; C10M 2219/046 20130101; C10N
2060/14 20130101; C10M 2227/09 20130101; C10N 2010/12 20130101;
C10M 2227/09 20130101; C10N 2010/12 20130101; C10M 2207/042
20130101; C10N 2060/14 20130101; C10M 2215/08 20130101; C10N
2060/14 20130101; C10M 2215/28 20130101; C10N 2060/14 20130101;
C10M 2219/044 20130101; C10N 2060/14 20130101; C10M 2219/046
20130101; C10N 2060/14 20130101 |
Class at
Publication: |
123/196.R ;
508/156; 508/186 |
International
Class: |
F01M 11/00 20060101
F01M011/00; C10M 169/04 20060101 C10M169/04 |
Claims
1. A lubricating oil composition having a sulfur content of up to
about 0.4 wt. % and a sulfated ash content of up to about 0.5 wt. %
as determined by ASTM D874 and comprising (a) a major amount of an
oil of lubricating viscosity; (b) at least one oil-soluble or
dispersed oil-stable boron-containing compound having from about 40
ppm to no more than about 400 ppm of boron, based upon the total
mass of the composition; and (c) at least one oil-soluble or
dispersed oil-stable molybdenum-containing compound having at least
about 1100 ppm of molybdenum, based upon the total mass of the
composition; wherein the lubricating oil composition has a ratio of
sulfur to molybdenum of about 0.5:1 to less than or equal to about
4:1.
2. The lubricating oil composition of claim 1, wherein the oil of
lubricating viscosity is comprised of a mineral base oil.
3.-4. (canceled)
5. The lubricating oil composition of claim 1, having a ratio of
sulfur to molybdenum of less than about 3:1.
6.-8. (canceled)
9. The lubricating oil composition of claim 1, having a ratio of
sulfur to molybdenum of about 1:1 to about 2.5:1.
10. The lubricating oil composition of claim 1, wherein the
oil-soluble or dispersed oil-stable molybdenum compound is selected
from the group consisting of a sulfurized or non-sulfurized
molybdenum polyisobutenyl succinimide complex, molybdenum
dithiocarbamate, dispersed hydrated molybdenum compound, acidic
molybdenum compound or a salt thereof and mixtures thereof.
11. (canceled)
12. The lubricating oil composition of claim 1, wherein the
oil-soluble or dispersed oil-stable molybdenum compound is a
molybdenum dithiocarbamate.
13. The lubricating oil composition of claim 1, wherein the
oil-soluble or dispersed oil-stable molybdenum compound is a
sulfurized or non-sulfurized molybdenum polyisobutenyl succinimide
complex.
14. The lubricating oil composition of claim 1, wherein the sulfur
is derived from a compound selected from the group consisting of a
polyisobutyl dithiothione, ashless dithiocarbamate and mixtures
thereof.
15. The lubricating oil composition of claim 1 wherein the sulfur
is derived from a bisdithiocarbamate compound of the Formula:
##STR00012## wherein R.sup.13, R.sup.14, R.sup.15, and R.sup.16 are
the same or different and are aliphatic hydrocarbyl groups having 1
to 13 carbon atoms and R.sup.17 is an alkylene group having 1 to 8
carbon atoms.
16. (canceled)
17. The lubricating oil composition of claim 1, having a sulfated
ash content of up to about 0.4 wt. % as determined by ASTM
D874.
18. The lubricating oil composition of claim 1, which is
substantially free of phosphorus.
19. The lubricating oil composition of claim 1, which is
substantially free of zinc dialkyl dithiophosphate.
20. The lubricating oil composition of claim 1, further comprising
at least one additive selected from the group consisting of
metallic detergents, ashless dispersants, friction modifiers,
extreme pressure agents, viscosity index improvers and pour point
depressants.
21. A method of operating an internal combustion engine comprising
the step of operating the internal combustion engine with a
lubricating oil composition having a sulfur content of up to about
0.4 wt. % and a sulfated ash content of up to about 0.5 wt. % as
determined by ASTM D874 and comprising (a) a major amount of an oil
of lubricating viscosity; (b) at least one oil-soluble or dispersed
oil-stable boron-containing compound having from about 40 ppm to no
more than about 400 ppm of boron, based upon the total mass of the
composition; and (c) at least one oil-soluble or dispersed
oil-stable molybdenum-containing compound having at least about
1100 ppm of molybdenum, based upon the total mass of the
composition; wherein the lubricating oil composition has a ratio of
sulfur to molybdenum of about 0.5:1 to less than or equal to about
4:1.
22-27. (canceled)
28. The method of claim 21, wherein the lubricating oil composition
has a ratio of sulfur to molybdenum of about 1:1 to about
2.5:1.
29. The method of claim 21, wherein the oil-soluble or dispersed
oil-stable molybdenum compound of the lubricating oil composition
is selected from the group consisting of a sulfurized or
non-sulfurized molybdenum polyisobutenyl succinimide complex,
molybdenum dithiocarbamate, dispersed hydrated molybdenum compound,
acidic molybdenum compound or a salt thereof and mixtures
thereof.
30. The method of claim 21, wherein the sulfur of the lubricating
oil composition is derived from a compound selected from the group
consisting of an alkyl or alkenyl sulfide, polyisobutyl
dithiothione, ashless dithiocarbamate and mixtures thereof.
31. (canceled)
32. The method of claim 21, wherein the sulfur of the lubricating
oil composition is derived from a bisdithiocarbamate compound of
the Formula: ##STR00013## wherein R.sup.13, R.sup.14, R.sup.15, and
R.sup.16 are the same or different and are aliphatic hydrocarbyl
groups having 1 to 13 carbon atoms and R.sup.17 is an alkylene
group having 1 to 8 carbon atoms.
33. (canceled)
34. The method of claim 21, wherein the lubricating oil composition
has a sulfated ash content of up to about 0.4 wt. % as determined
by ASTM D874.
35. The method of claim 21, wherein the lubricating oil composition
is substantially free of phosphorus.
36. The method of claim 21, wherein the lubricating oil composition
is substantially free of zinc dialkyl dithiophosphate.
37. An internal combustion engine lubricated with the lubricating
oil composition of claim 1.
38.-39. (canceled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention generally relates to lubricating oil
compositions.
[0003] 2. Description of the Related Art
[0004] Exhaust after-treatment devices, equipped on internal
combustion engines to comply with emission regulations, have proven
to be sensitive to the combustion by products of the fuel and
lubricant used in the engine. In addition, certain types of devices
are sensitive to one or more of the following: (1) phosphorus
coming from the lubricant, (2) sulfur coming from both fuel and
lubricant, and (3) sulfated ash resulting from the combustion of
fuel and lubricant. In order to ensure the durability of the
different types of after-treatment devices, special lubricants are
being developed that feature relatively low levels of, for example,
sulfur, phosphorus, and sulfated ash.
[0005] U.S. Patent Application Publication. No. 20050043191 ("the
'191 application") discloses a lubricating oil composition having
less than 2000 ppm sulfur and free of zinc and phosphorus. The '191
application further discloses that the lubricating oil composition
has a minimum of 120 ppm of boron and a minimum of 80 ppm of
molybdenum. Each of the examples shown in Table 1 of the '191
application disclose an ash content of 0.96, 0.99 and 1.05 for Oils
1, 2, and 3, respectively.
[0006] U.S. Pat. No. 6,777,378 ("the '378 patent") discloses a
lubricating oil composition containing (a) a base oil; (b) a
molybdenum- and sulfur-containing composition derived from a basic
nitrogen-containing compound, a molybdenum compound and carbon
disulfide; (c) a borate ester; and (d) optionally a
phosphorus-containing compound provided that the phosphorus content
of the composition does not exceed about 0.10 wt. %. The '378
patent further discloses that the lubricating oil composition has a
boron content of about 30 ppm to about 600 ppm and a molybdenum
content of about 25 ppm to about 800 ppm.
[0007] U.S. Pat. No. 7,026,273 ("the '273 patent") discloses a
lubricating oil composition containing a major amount of oil of
lubricating viscosity, and a minor amount of a boron-containing
additive, a detergent additive composition and one or more
co-additives. The '273 patent further discloses that the
lubricating oil composition has a boron content of greater than 150
ppm, a molybdenum content of at most 1000 ppm and less than 4000
ppm by mass of sulfur.
[0008] EP 0 737 735 ("the 735 application") discloses a lubricant
composition produced by blending (a) a Mo-containing friction
conditioner; and (b) a B-containing compound with a lubricant base
oil. The 735 application further discloses that the lubricating oil
composition has a boron content of greater than 0.015 wt. % (150
ppm) and a molybdenum content of 100 ppm to 2000 ppm.
[0009] It is desirable to develop improved lubricating oil
compositions which exhibit improved deposit reduction, as well as
wear and oxidation inhibition when used in an internal combustion
engine.
SUMMARY OF THE INVENTION
[0010] In accordance with one embodiment of the present invention,
a lubricating oil composition having a sulfur content of up to
about 0.4 wt. % and a sulfated ash content of up to about 0.5 wt. %
as determined by ASTM D874 is provided which comprises (a) a major
amount of an oil of lubricating viscosity; (b) at least one
oil-soluble or dispersed oil-stable boron-containing compound
having no more than about 400 ppm of boron, based upon the total
mass of the composition; and (c) at least one oil-soluble or
dispersed oil-stable molybdenum-containing compound having at least
about 1100 ppm of molybdenum, based upon the total mass of the
composition; wherein the lubricating oil composition has a ratio of
sulfur to molybdenum of less than or equal to about 4:1.
[0011] In accordance with a second embodiment of the present
invention, there is provided a method of operating an internal
combustion engine which comprises operating the internal combustion
engine with a lubricating oil composition having a sulfur content
of up to about 0.4 wt. % and a sulfated ash content of up to about
0.5 wt % as determined by ASTM D874 and comprising (a) a major
amount of an oil of lubricating viscosity; (b) at least one
oil-soluble or dispersed oil-stable boron-containing compound
having no more than about 400 ppm of boron, based upon the total
mass of the composition; and (c) at least one oil-soluble or
dispersed oil-stable molybdenum-containing compound having at least
about 1100 ppm of molybdenum, based upon the total mass of the
composition; wherein the lubricating oil composition has a ratio of
sulfur to molybdenum of less than or equal to about 4:1.
[0012] In accordance with a third embodiment of the present
invention, there is provided an internal combustion engine
lubricated with a lubricating oil composition having a sulfur
content of up to about 0.4 wt. % and a sulfated ash content of up
to about 0.5 wt. % as determined by ASTM D874 and comprising (a) a
major amount of an oil of lubricating viscosity; (b) at least one
oil-soluble or dispersed oil-stable boron-containing compound
having no more than about 400 ppm of boron, based upon the total
mass of the composition; and (c) at least one oil-soluble or
dispersed oil-stable molybdenum-containing compound having at least
about 1100 ppm of molybdenum, based upon the total mass of the
composition; wherein the lubricating oil composition has a ratio of
sulfur to molybdenum of less than or equal to about 4:1.
[0013] The molybdenum-containing lubricating oil compositions of
the present invention advantageously provide high wear inhibition
when used in an internal combustion engine while containing
relatively low levels of sulfated ash content. In addition, the
high wear inhibition can be achieved with the molybdenum-containing
lubricating oil compositions of the present invention while also
employing relatively low levels (or substantially free) of any
phosphorus and zinc content.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] The present invention is directed to a lubricating oil
composition having a sulfur content of up to about 0.4 wt. % and a
sulfated ash content of up to about 0.5 wt. % as determined by ASTM
D874 and containing at least (a) a major amount of an oil of
lubricating viscosity; (b) at least one oil-soluble or dispersed
oil-stable boron-containing compound having no more than about 400
ppm of boron, based upon the total mass of the composition; and (c)
at least one oil-soluble or dispersed oil-stable
molybdenum-containing compound having at least about 1100 ppm of
molybdenum, based upon the total mass of the composition; wherein
the lubricating oil composition has a ratio of sulfur to molybdenum
of less than or equal to about 4:1. In one embodiment, the
lubricating oil composition of the present invention has a sulfur
content of up to about 0.3 wt. %, and/or sulfated ash content of up
to about 0.4 wt. % as determined by ASTM D874. The amount of
sulfur, boron, molybdenum or phosphorus in the lubricating oil
composition of the present invention is measured according to ASTM
D4951.
[0015] The oil of lubricating viscosity for use in the lubricating
oil compositions of this invention, also referred to as a base oil,
is typically present in a major amount, e.g., an amount of greater
than 50 wt. %, preferably greater than about 70 wt. %, more
preferably from about 80 to about 99.5 wt. % and most preferably
from about 80 to about 98 wt. %, based on the total weight of the
composition. The expression "base oil" as used herein shall be
understood to mean a base stock or blend of base stocks which is a
lubricant component that is produced by a single manufacturer to
the same specifications (independent of feed source or
manufacturer's location); that meets the same manufacturer's
specification; and that is identified by a unique formula, product
identification number, or both. The base oil for use herein can be
any presently known or later-discovered oil of lubricating
viscosity used in formulating lubricating oil compositions for any
and all such applications, e.g., engine oils, marine cylinder oils,
functional fluids such as hydraulic oils, gear oils, transmission
fluids, etc. For example, the base oils can be used in formulating
lubricating oil compositions for any and all such applications such
as passenger car engine oils, heavy duty diesel motor oils and
natural gas engine oils. Additionally, the base oils for use herein
can optionally contain viscosity index, improvers, e.g., polymeric
alkylmethacrylates; olefinic copolymers, e.g., an
ethylene-propylene copolymer or a styrene-butadiene copolymer; and
the like and mixtures thereof.
[0016] As one skilled in the art would readily appreciate, the
viscosity of the base oil is dependent upon the application.
Accordingly, the viscosity of a base oil for use herein will
ordinarily range from about 2 to about 2000 centistokes (cSt) at
100.degree. Centigrade (C). Generally, individually the base oils
used as engine oils will have a kinematic viscosity range at
100.degree. C. of about 2 cSt to about 30 cSt, preferably about 3
cSt to about 16 cSt, and most preferably about 4 cSt to about 12
cSt and will be selected or blended depending on the desired end
use and the additives in the finished oil to give the desired grade
of engine oil, e.g., a lubricating oil composition having an SAE
Viscosity Grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W,
5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40,
10W-50, 15W, 15W-20, 15W-30 or 15W-40. Oils used as gear oils can
have viscosities ranging from about 2 cSt to about 2000 cSt at
100.degree. C.
[0017] Base stocks may be manufactured using a variety of different
processes including, but not limited to, distillation, solvent
refining, hydrogen processing, oligomerization, esterification, and
rerefining. Rerefined stock shall be substantially free from
materials introduced through manufacturing, contamination, or
previous use. The base oil of the lubricating oil compositions of
this invention may be any natural or synthetic lubricating base
oil. Suitable hydrocarbon synthetic oils include, but are not
limited to, oils prepared from the polymerization of ethylene or
from the polymerization of 1-olefins to provide polymers such as
polyalphaolefin or PAO oils, or from hydrocarbon synthesis
procedures using carbon monoxide and hydrogen gases such as in a
Fischer-Tropsch process. For example, a suitable base oil is one
that comprises little, if any, heavy fraction; e.g., little, if
any, lube oil fraction of viscosity 20 cSt or higher at 100.degree.
C.
[0018] 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 hydrocracked 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. Group IV
base oils are polyalphaolefins (PAO). Group V base oils include all
other base oils not included in Group I, II, III, or IV. Although
Group II, III and IV base oils are preferred for use in this
invention, these base oils may be prepared by combining one or more
of Group I, II, III, IV and V base stocks or base oils.
[0019] Useful natural oils include mineral lubricating oils such
as, for example, liquid petroleum oils, solvent-treated or
acid-treated mineral lubricating oils of the paraffinic, naphthenic
or mixed paraffinic-naphthenic types, oils derived from coal or
shale, animal oils, vegetable oils (e.g., rapeseed oils, castor
oils and lard oil), and the like.
[0020] Useful synthetic lubricating oils include, but are not
limited to, hydrocarbon oils and halo-substituted hydrocarbon oils
such as polymerized and interpolymerized olefins, e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes),
poly(1-decenes), and the like and mixtures thereof, alkylbenzenes
such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,
di(2-ethylhexyl)-benzenes, and the like, polyphenyls such as
biphenyls, terphenyls, alkylated polyphenyls, and the like,
alkylated diphenyl ethers and alkylated diphenyl sulfides and the
derivative, analogs and homologs thereof and the like.
[0021] Other useful synthetic lubricating oils include, but are not
limited to, oils made by polymerizing olefins of less than 5 carbon
atoms such as ethylene, propylene, butylenes, isobutene, pentene,
and mixtures thereof. Methods of preparing such polymer oils are
well known to those skilled in the art.
[0022] Additional useful synthetic hydrocarbon oils include liquid
polymers of alpha olefins having the proper viscosity. Especially
useful synthetic hydrocarbon oils are the hydrogenated liquid
oligomers of C.sub.6 to C.sub.12 alpha olefins such as, for
example, 1-decene trimer.
[0023] Another class of useful synthetic lubricating oils include,
but are not limited to, alkylene oxide polymers, i.e.,
homopolymers, interpolymers, and derivatives thereof where the
terminal hydroxyl groups have been modified by, for example,
esterification or etherification. These oils are exemplified by the
oils prepared through polymerization of ethylene oxide or propylene
oxide, the alkyl and phenyl ethers of these polyoxyalkylene
polymers (e.g., methyl poly propylene glycol ether having an
average molecular weight of 1,000, diphenyl ether of polyethylene
glycol having a molecular weight of 500-1000, diethyl ether of
polypropylene glycol having a molecular weight of 1,000-1,500,
etc.) or mono- and polycarboxylic esters thereof such as, for
example, the acetic esters, mixed C.sub.3-C.sub.8 fatty acid
esters, or the C.sub.13 oxo, acid diester of tetraethylene
glycol.
[0024] Yet another class of useful synthetic lubricating oils
include, but are not limited to, the esters of dicarboxylic acids
e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl
succinic acids, maleic acid, azelaic acid, suberic acid, sebacic
acid, fumaric acid, adipic acid, linoleic acid dimer, malonic
acids, alkyl malonic acids, alkenyl malonic acids, etc., with a
variety of alcohols, e.g., butyl alcohol, hexyl alcohol, dodecyl
alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol
monoether, propylene glycol, etc. Specific examples of these esters
include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,
dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the
2-ethylhexyl diester of linoleic acid dimer, the complex ester
formed by reacting one mole of sebacic acid with two moles of
tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the
like.
[0025] Esters useful as synthetic oils also include, but are not
limited to, those made from carboxylic acids having from about 5 to
about 12 carbon atoms with alcohols, e.g., methanol, ethanol, etc.,
polyols and polyol ethers such as neopentyl glycol, trimethylol
propane, pentaerythritol, dipentaerythritol, tripentaerythritol,
and the like.
[0026] Silicon-based oils such as for example, polyalkyl-,
polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate
oils, comprise another useful class of synthetic lubricating oils.
Specific examples of these include, but are not limited to,
tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl)
silicate, tetra-(4-methyl-hexyl)silicate,
tetra-(p-tert-butylphenyl)silicate,
hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes,
poly(methylphenyl)siloxanes, and the like. Still yet other useful
synthetic lubricating oils include, but are not limited to liquid
esters of phosphorus containing acids, e.g., tricresyl phosphate,
trioctyl phosphate, diethyl ester of decane phosphionic acid, etc.,
polymeric tetrahydrofurans, and the like.
[0027] The lubricating oil may be derived from unrefined, refined
and rerefined oils, either natural, synthetic or mixtures of two or
more of any of these of the type disclosed hereinabove. Unrefined
oils are those obtained directly from a natural or synthetic source
(e.g., coal, shale, or tar sands bitumen) without further
purification or treatment. Examples of unrefined oils include, but
are not limited to, a shale oil obtained directly from retorting
operations, a petroleum oil obtained directly from distillation or
an ester oil obtained directly from an esterification process, each
of which is then used without further treatment. Refined oils are
similar to the unrefined oils except they have been further treated
in one or more purification steps to improve one or more
properties. These purification techniques are known to those of
skill in the art and include, for example, solvent extractions,
secondary distillation, acid or base extraction, filtration,
percolation, hydrotreating, dewaxing, etc. Rerefined oils are
obtained by treating used oils in processes similar to those used
to obtain refined oils. Such rerefined oils are also known as
reclaimed or reprocessed oils and often are additionally processed
by techniques directed to removal of spent additives and oil
breakdown products.
[0028] Lubricating oil base stocks derived from the
hydroisomerization of wax may also be used, either alone or in
combination with the aforesaid natural and/or synthetic base
stocks. Such wax isomerate oil is produced by the
hydroisomerization of natural or synthetic waxes or mixtures
thereof over a hydroisomerization catalyst.
[0029] Natural waxes are typically the slack waxes recovered by the
solvent dewaxing of mineral oils; synthetic waxes are typically the
wax produced by the Fischer-Tropsch process.
The Oil-Soluble or Dispersed Oil-Stable Boron-Containing
Compound
[0030] Representative examples of at least one oil-soluble or
dispersed oil-stable boron-containing compound for use in the
lubricating oil compositions of the present invention include a
borated dispersant; a borated friction modifier; a dispersed alkali
metal or a mixed alkali metal or an alkaline earth metal borate, a
borated epoxide, a borate ester, a borated fatty amine, a borated
amide, a borated sulfonate, and the like, and mixtures thereof.
[0031] Examples of borated dispersants include, but are not limited
to, borated ashless dispersants such as the borated polyalkenyl
succinic anhydrides; borated non-nitrogen containing derivatives of
a polyalkylene succinic anhydride; a borated basic nitrogen
compound selected from the group consisting of succinimides,
carboxylic acid amides, hydrocarbyl monoamines, hydrocarbyl
polyamines, Mannich bases, phosphonoamides, thiophosphonamides and
phosphoramides, thiazoles, e.g., 2,5-dimercapto-1,3,4-thiadiazoles,
mercaptobenzothiazoles and derivatives thereof, triazoles, e.g.,
alkyltriazoles and benzotriazoles, copolymers which contain a
carboxylate ester with one or more additional polar function,
including amine, amide, imine, imide, hydroxyl, carboxyl, and the
like, e.g., products prepared by copolymerization of long chain
alkyl acrylates or methacrylates with monomers of the above
function; and the like and mixtures thereof. A preferred borated
dispersant is a succinimide derivative of boron such as, for
example, a borated polyisobutenyl succinimide.
[0032] Examples of borated friction modifiers include, but are not
limited to, borated fatty epoxides, borated alkoxylated fatty
amines, borated glycerol esters and the like and mixtures
thereof.
[0033] The hydrated particulate alkali metal borates are well known
in the art and are available commercially. Representative examples
of hydrated particulate alkali metal borates and methods of
manufacture include those disclosed in, e.g., U.S. Pat. Nos.
3,313,727; 3,819,521; 3,853,772; 3,907,601; 3,997,454; 4,089,790;
6,737,387 and 6,534,450, the contents of which are incorporated
herein by reference. The hydrated alkali metal borates can be
represented by the following Formula:
M.sub.2O.mB.sub.2O.sub.3.nH.sub.2O where M is an alkali metal of
atomic number in the range of about 11 to about 19, e.g., sodium
and potassium; m is a number from about 2.5 to about 4.5 (both
whole and fractional); and n is a number from about 1.0 to about
4.8. Preferred are the hydrated sodium borates. The hydrated borate
particles generally have a mean particle size of less than about 1
micron.
[0034] Examples of borated epoxides include borated epoxides
obtained from the reaction product of one or more of the boron
compounds with at least one epoxide. Suitable boron compounds
include boron oxide, boron oxide hydrate, boron trioxide, boron
trifluoride, boron tribromide, boron trichloride, boron acids such
as boronic acid, boric acid, tetraboric acid and metaboric acid,
boron amides and various esters of boron acids. The epoxide is
generally an aliphatic epoxide having from about 8 to about 30
carbon atoms and preferably from about 10 to about 24 carbon atoms
and more preferably from about 12 to about 20 carbon atoms.
Suitable aliphatic epoxides include dodecene oxide, hexadecene
oxide and the like and mixtures thereof. Mixtures of epoxides may
also be used, for instance commercial mixtures of epoxides having
from about 14 to about 16 carbon atoms or from about 14 to about 18
carbon atoms. The borated epoxides are generally known and
described in, for example, U.S. Pat. No. 4,584,115.
[0035] Examples of borate esters include those borate esters
obtained by reacting one or more of the boron compounds disclosed
above with one or more alcohols of suitable oleophilicity.
Typically, the alcohols will contain from 6 to about 30 carbons and
preferably from 8 to about 24 carbon atoms. The methods of making
such borate esters are well known in the art. The borate esters can
also be borated phospholipids. Representative examples of borate
esters include those having the structures set forth in Formulae
I-III:
##STR00001##
wherein each R is independently a C.sub.1-C.sub.12 straight or
branched alkyl group and R.sup.1 is hydrogen or a C.sub.1-C.sub.12
straight or branched alkyl group.
[0036] Examples of borated fatty amines include borated fatty
amines obtained by reacting one or more of the boron compounds
disclosed above with one or more of fatty amines, e.g., an amine
having from about fourteen to about eighteen carbon atoms. The
borated fatty amines may be prepared by reacting the amine with the
boron compound at a temperature in the range of from about 50 to
about 300.degree. C., and preferably from about 100 to about
250.degree. C., and at a ratio from about 3:1 to about 1:3
equivalents of amine to equivalents of boron compound.
[0037] Examples of borated amides include borated amides obtained
from the reaction product of a linear or branched, saturated or
unsaturated monovalent aliphatic acid having 8 to about 22 carbon
atoms, urea, and polyalkylenepolyamine with a boric acid compound
and the like and mixtures thereof.
[0038] Examples of borated sulfonates include borated alkaline
earth metal sulfonates obtained by (a) reacting in the presence of
a hydrocarbon solvent (i) at least one of an oil-soluble sulfonic
acid or alkaline earth sulfonate salt or mixtures thereof; (ii) at
least one source of an alkaline earth metal; (iii) at least one
source of boron, and (iv) from 0 to less than 10 mole percent,
relative to the source of boron, of an overbasing acid, other than
the source of boron; and (b) heating the reaction product of (a) to
a temperature above the distillation temperature of the hydrocarbon
solvent to distill the hydrocarbon solvent and water from the
reaction. Suitable borated alkaline earth metal sulfonates include
those disclosed in, for example, U.S. Patent Application
Publication No. 20070123437, the contents of which are incorporated
by reference herein.
[0039] The lubricating oil compositions of the present invention
will contain no more than about 400 ppm of boron, based upon the
total mass of the composition, provided from the one or more
oil-soluble or dispersed oil-stable boron-containing compounds. In
one embodiment, the lubricating oil compositions of the present
invention will contain no more than about 300 ppm of boron, based
upon the total mass of the composition, provided from the one or
more oil-soluble or dispersed oil-stable boron-containing
compounds. In another embodiment, the lubricating oil compositions
of the present invention will contain no more than about 200 ppm of
boron, based upon the total mass of the composition, provided from
the one or more oil-soluble or dispersed oil-stable
boron-containing compounds. In yet another embodiment, the
lubricating oil compositions of the present invention will contain
no more than about 100 ppm of boron, based upon the total mass of
the composition, provided from the one or more oil-soluble or
dispersed oil-stable boron-containing compounds. In another
embodiment, the lubricating oil compositions of the present
invention will contain from about 40 ppm to no more than about 400
ppm of boron, based upon the total mass of the composition,
provided from the one or more oil-soluble or dispersed oil-stable
boron-containing compounds. In still yet another embodiment, the
lubricating oil compositions of the present invention will be
substantially free of any boron content.
The Oil-Soluble or Dispersed Oil-Stable Molybdenum-Containing
Compound
[0040] Representative examples of at least one oil-soluble or
dispersed oil-stable molybdenum-containing compound for use in the
lubricating oil compositions of the present invention include
molybdenum dithiocarbamates; molybdenum dithiophosphates; dispersed
hydrated molybdenum compounds; acidic molybdenum compounds or salts
of acidic molybdenum compounds; molybdenum-containing complexes and
the like and mixtures thereof.
[0041] Examples of dispersed hydrated molybdenum, compounds include
dispersed hydrated polymolybdates, dispersed hydrated alkali metal
polymolybdates and the like and mixtures thereof. Suitable
dispersed hydrated polymolybdates include those disclosed in, for
example, U.S. Patent Application Publication No. 20050070445, the
contents of which are incorporated by reference herein.
[0042] Suitable molybdenum dithiocarbamates include any molybdenum
dithiocarbamate which can be used as an additive for lubricating
oils. One class of molybdenum dithiocarbamates for use herein is
represented by Formula IV:
##STR00002##
wherein R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each
independently: hydrogen or a hydrocarbon group including, by way of
example, alkyl groups, alkenyl groups, aryl groups, cycloalkyl
groups and cycloalkenyl groups, and X.sup.1, X.sup.2, X.sup.3 and
X.sup.4 are each independently sulfur or oxygen.
[0043] Suitable alkyl groups include, but are not limited to,
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl,
tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl,
tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl,
octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl,
decyl, secondary decyl, undecyl, secondary undecyl, dodecyl,
secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl,
tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl,
stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl,
2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl,
2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl,
2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl,
monomethyl branched-isostearyl and the like.
[0044] Suitable alkenyl groups include, but are not limited to,
vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl,
hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
tetradecenyl, oleyl and the like.
[0045] Suitable aryl groups include, but are not limited to,
phenyl, tolyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl,
cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl,
butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl,
nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, biphenyl,
benzylphenyl, styrenated phenyl, p-cumylphenyl, alpha-naphthyl,
beta-naphthyl groups and the like.
[0046] Suitable cycloalkyl groups and cycloalkenyl groups include,
but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl,
methylcyclopentyl, methylcyclohexyl, methylcycloheptyl,
cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl,
methylcyclohexenyl, methylcycloheptenyl groups and the like.
[0047] Of these groups, the alkyl groups or alkenyl groups are
preferred as R.sup.2 to R.sup.5 in Formula IV. Preferably, the R
groups in Formula IV are identical groups.
[0048] In Formula IV, X.sup.1 to X.sup.4 are independently selected
from sulfur or oxygen atom, and all of X.sup.1 to X.sup.4 may be a
sulfur atom or an oxygen atom, or a mixture of sulfur atoms and
oxygen atoms. In consideration of balance between friction reducing
effect and corrosivity, the molar ratio (ratio of numbers) of
sulfur atom(s)/oxygen atom(s) should particularly preferably be in
the range from about 1/3 to about 3/1.
[0049] Some of the oil-soluble or dispersed oil-stable molybdenum
compounds of Formula IV are commercially available. For example,
products where X.sup.1 and X.sup.2 are O, X.sup.3 and X.sup.4 are
S, and where R.sup.2 to R.sup.5 are C.sub.13H.sub.27 aliphatic
hydrocarbyl groups and where the molybdenum is in oxidation state V
are sold under the trademarks Molyvan 807 and Molyvan 822 as
antioxidants and friction reducing additives by R.T. Vanderbilt
Company Inc. (Norwalk, Conn. USA). These molybdenum compounds may
be prepared by the methods described in U.S. Pat. No. 3,356,702
wherein MoO.sub.3 is converted to soluble molybdate by dissolving
in alkali metal hydroxide solution, neutralized by the addition of
acid followed by the addition of a secondary amine and carbon
disulfide. In another aspect, the molybdenum compounds of Formula I
wherein X.sup.1 to X.sup.4 are O or S may be prepared by a number
of methods known in the art such as, for example, U.S. Pat. Nos.
4,098,705 and 5,631,213.
[0050] Generally, the sulfurized oxymolybdenum dithiocarbamates
represented by Formula IV can be prepared by reacting molybdenum
trioxide or a molybdate with an alkali sulfide or an alkali
hydrosulfide, and subsequently, adding carbon disulfide and a
secondary amine to the reaction mixture and reacting the resultant
mixture at an adequate temperature. To prepare the asymmetric
sulfurized oxymolybdenum dithiocarbamates, the use of a secondary
amine having different hydrocarbon groups or the use of two or more
different secondary amines in the above process is sufficient. The
symmetric sulfurized oxymolybdenum dithiocarbamates can also be
prepared in a similar manner, but with the use of only one
secondary amine.
[0051] Examples of suitable molybdenum dithiocarbamate compounds
include, but are not limited to, sulfurized molybdenum
diethyldithiocarbamate, sulfurized molybdenum
dipropyldithiocarbamate, sulfurized molybdenum
dibutyldithiocarbamate, sulfurized molybdenum
dipentyldithiocarbamate, sulfurized molybdenum
dihexyldithiocarbamate, sulfurized molybdenum
dioctyldithiocarbamate, sulfurized molybdenum
didecyldithiocarbamate, sulfurized molybdenum
didodecyldithiocarbamate, sulfurized molybdenum
ditridecyldithiocarbamate, sulfurized molybdenum
di(butylphenyl)dithiocarbamate, sulfurized molybdenum
di(nonylphenyl)dithiocarbamate, sulfurized oxymolybdenum
diethyldithiocarbamate, sulfurized oxymolybdenum
dipropyldithiocarbamate, sulfurized oxymolybdenum
dibutyldithiocarbamate, sulfurized oxymolybdenum
dipentyldithiocarbamate, sulfurized oxymolybdenum
dihexyldithiocarbamate, sulfurized oxymolybdenum
dioctyldithiocarbamate, sulfurized oxymolybdenum
didecyldithiocarbamate, sulfurized oxymolybdenum
didodecyldithiocarbamate, sulfurized oxymolybdenum
ditridecyldithiocarbamate, sulfurized oxymolybdenum
di(butylphenyl)dithiocarbamate, sulfurized oxymolybdenum
di(nonylphenyl)dithiocarbamate, all of which the alkyl groups may
be straight-chain or branched, and the like and mixtures
thereof.
[0052] Suitable molybdenum dithiophosphates include any molybdenum
dithiophosphate which can be used as an additive for lubricating
oils. Examples of suitable molybdenum dithiophosphates include
molybdenum dialkyl or diaryl dithiophosphate such as molybdenum
diisopropyldithiophosphate, molybdenum
di-(2-ethylhexyl)dithiophosphate, molybdenum
di-(nonylphenyl)dithiophosphate and the like and mixtures
thereof.
[0053] The molybdenum-containing complexes may be generally
characterized as containing a molybdenum or molybdenum/sulfur
complex of a basic nitrogen compound. The
molybdenum/nitrogen-containing complexes employed herein are well
known in the art and are complexes of molybdic acid and an
oil-soluble basic nitrogen-containing compound. Generally, the
molybdenum/nitrogen-containing complex can be made with an organic
solvent comprising a polar promoter during a complexation step and
procedures for preparing such complexes are described, for example,
in U.S. Pat. Nos. 4,259,194; 4,259,195; 4,261,843; 4,263,152;
4,265,773; 4,283,295; 4,285,822; 4,369,119; 4,370,246; 4,394,279;
4,402,840; and 6,962,896 and U.S. Patent Application Publication
No. 2005/0209111. As shown in these references the
molybdenum/nitrogen-containing complex can further be
sulfurized.
[0054] In another embodiment, a molybdated succinimide complex can
be prepared by a process which involves at least (a) reacting an
alkyl or alkenyl succinimide of a polyamine of Formula V:
##STR00003##
wherein R.sup.6 is an about C.sub.12 to about C.sub.30 alkyl or
alkenyl group; a and b are independently 2 or 3, and x is 0 to 10,
preferably 1 to 6 and more preferably 2 to 5; with an ethylenically
unsaturated carboxylic acid and/or anhydride thereof; and (b)
reacting the succinimide product of step (a) with an acidic
molybdenum compound, e.g., as disclosed in U.S. patent application
Ser. No. 12/215,723, filed on Jun. 30, 2008, the contents of which
are incorporated by reference herein. In one embodiment, the
R.sup.6 substituent has a number average molecular weight ranging
from about 167 to about 419 and preferably from about 223 to about
279. In another embodiment, R.sup.6 is an about C.sub.12 to about
C.sub.24 alkyl or alkenyl group; a and b are each 2; and x is 2 to
5.
[0055] In step (a), a succinimide of Formula V:
##STR00004##
wherein R.sup.6, a, b and x have the aforestated meanings, is
reacted with an ethylenically unsaturated carboxylic acid. The
starting succinimide of Formula V can be obtained by reacting an
anhydride of Formula VI:
##STR00005##
wherein R.sup.6 has the aforestated meaning with a polyamine. The
anhydride of Formula VI is either commercially available from such
sources as, for example, Sigma Aldrich Corporation (St. Louis, Mo.,
U.S.A.), or can be prepared by any method well known in the
art.
[0056] Suitable polyamines for use in preparing the succinimide of
Formula V are polyalkylene polyamines, including polyalkylene
diamines. Such polyalkylene polyamines will typically contain about
2 to about 12 nitrogen atoms and about 2 to 24 carbon atoms.
Particularly suitable polyalkylene polyamines are those having the
Formula: H.sub.2N--(R.sup.7NH).sub.c--H wherein R.sup.7 is a
straight- or branched-chain alkylene group having 2 or 3 carbon
atoms and c is 1 to 9. Representative examples of suitable
polyalkylene polyamines include ethylenediamine,
diethylenetriamine, triethylenetetraamine, tetraethylenepentamine,
and mixtures thereof. Most preferably, the polyalkylene polyamine
is tetraethylenepentamine.
[0057] Many of the polyamines suitable for use in the present
invention are commercially available and others may be prepared by
methods which are well known in the art. For example, methods for
preparing amines and their reactions are detailed in Sidgewick's
"The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966;
Noller's "Chemistry of Organic Compounds", Saunders, Philadelphia,
2nd Ed., 1957; and Kirk-Othmer's "Encyclopedia of Chemical
Technology", 2nd Ed., especially Volume 2, pp. 99-116.
[0058] Generally, the anhydride of Formula VI is reacted with the
polyamine at a temperature of about 130.degree. C. to about
220.degree. C. and preferably from about 145.degree. C. to about
175.degree. C. The reaction can be carried out under an inert
atmosphere, such as nitrogen or argon. The amount of anhydride of
Formula VI employed in the reaction can range from about 30 to
about 95 wt. % and preferably from about 40 to about 60 wt. %,
based on the total weight of the reaction mixture.
[0059] Suitable ethylenically unsaturated carboxylic acids or their
anhydrides include ethylenically unsaturated monocarboxylic acids
or their anhydrides, ethylenically unsaturated dicarboxylic acids
or their anhydrides and the like and mixtures thereof. Useful
monocarboxylic acids or their anhydrides include, but are not
limited to, acrylic acid, methacrylic acid, and the like and
mixtures thereof. Useful ethylenically unsaturated dicarboxylic
acids or their anhydrides include, but are not limited to, fumaric
acid, maleic anhydride, mesaconic acid, citraconic acid, citraconic
anhydride, itaconic acid, itaconic anhydride, and the like and
mixtures thereof. A preferred ethylenically unsaturated carboxylic
acid or anhydride thereof is maleic anhydride or a derivative
thereof. This and similar anhydrides bond onto the succinimide
starting compound to provide a carboxylic acid functionality. The
treatment of the succinimide of Formula V with the ethylenically
unsaturated carboxylic acid or anhydrides thereof advantageously
allows for a sufficient amount of the molybdenum compound to be
incorporated into the complex.
[0060] Generally, the ethylenically unsaturated carboxylic acid or
its anhydride is heated to a molten condition at a temperature in
the range of from about 50.degree. C. to about 100.degree. C. and
is thereafter mixed with the succinimide of Formula V. The molar
ratio of ethylenically unsaturated carboxylic acid or its anhydride
to succinimide of Formula V will vary widely, e.g., a range of from
about 0.1:1 to about 2:1. In one embodiment, the charge molar ratio
of ethylenically unsaturated carboxylic acid or its anhydride to
succinimide of Formula V will range of from about 0.9:1 to about
1.05:1.
[0061] The molybdenum compounds used to prepare the molybdated
succinimide complex of the present invention are acidic molybdenum
compounds or salts of acidic molybdenum compounds. Generally, these
molybdenum compounds are hexavalent. Representative examples of
suitable molybdenum compounds can be any of the acid molybdenum
compounds discussed above. Particularly preferred is molybdenum
trioxide.
[0062] In step (b), a mixture of the succinimide product of step
(a) and acidic molybdenum compound is prepared with or without a
diluent. A diluent is used, if necessary, to provide a suitable
viscosity for stirring. Suitable diluents are lubricating oils and
liquid compounds containing only carbon and hydrogen. If desired,
ammonium hydroxide may also be added to the reaction mixture to
provide a solution of ammonium molybdate.
[0063] Generally, the reaction mixture is heated at a temperature
less than or equal to about 100.degree. C. and preferably from
about 80.degree. C. to about 100.degree. C. until the molybdenum is
sufficiently reacted. The reaction time for this step is typically
in the range of about 15 minutes to about 5 hours and preferably
about 1 to about 2 hours. The molar ratio of the molybdenum
compound to the succinimide product of step (a) is about 0.1:1 to
about 2:1, preferably from about 0.5:1 to about 1.5:1 and most
preferably about 1:1. Any water present following the reaction of
the molybdenum compound and succinimide product of step (a) can be
removed by heating the reaction mixture to a temperature greater
than about 100.degree. C., and preferably from about 120.degree. C.
to about 160.degree. C.
[0064] In another embodiment, a molybdated succinimide complex can
be prepared by a process which involves at least (a) reacting a
succinimide of a polyamine of Formula VII:
##STR00006##
wherein R.sup.8 is a hydrocarbon radical having a number average
molecular weight of about 500 to about 5,000; preferably a number
average molecular weight of about 700 to about 2,500 and more
preferably a number average molecular weight of about 710 to about
1,100; a and b are independently 2 or 3; and x is 0 to 10,
preferably 1 to 6 and more preferably 2 to 5, with an ethylenically
unsaturated carboxylic acid or anhydride thereof, in a charge mole
ratio of the ethylenically unsaturated carboxylic acid or anhydride
thereof to the succinimide of Formula VII of about 0.9:1 to about
1.05:1; and (b) reacting the succinimide product of step (a) with
an acidic molybdenum compound, e.g., as disclosed in U.S. patent
application Ser. No. 12/215,739, filed on Jun. 30, 2008, the
contents of which are incorporated by reference herein. In one
embodiment, R.sup.8 is an alkyl or alkenyl group. In another
embodiment, R.sup.8 is a polyalkenyl group. A preferred polyalkenyl
group is a polyisobutenyl group.
[0065] In step (a), a succinimide of Formula VII:
##STR00007##
wherein R.sup.8, a, b and x have the aforestated meanings, is
reacted with an ethylenically unsaturated carboxylic-acid in a
charge mole ratio of the ethylenically unsaturated carboxylic acid
or anhydride thereof to the succinimide of Formula I of about 0.9:1
to about 1.05:1. The starting succinimide of Formula VII can be
obtained by reacting an anhydride of Formula VIII:
##STR00008##
wherein R.sup.8 has the aforestated meaning with a polyamine. The
anhydride of Formula VIII is either commercially available from
such sources as, for example, Sigma Aldrich Corporation (St. Louis,
Mo., U.S.A.), or can be prepared by any method well known in the
art.
[0066] Suitable polyamines for use in preparing the succinimide of
Formula VII can be any of the polyamines disclosed herein above for
making the succinimide of Formula V. Preferably, the polyalkylene
polyamine is tetraethylenepentamine.
[0067] Generally, the anhydride of Formula VIII is reacted with the
polyamine at a temperature of about 130.degree. C. to about
220.degree. C. and preferably from about 145.degree. C. to about
175.degree. C. The reaction can be carried out under an inert
atmosphere, such as nitrogen or argon. The amount of anhydride of
Formula VIII employed in the reaction can range from about 30 to
about 95 wt % and preferably from about 40 to about 60 wt %, based
on, the total weight of the reaction mixture.
[0068] Suitable ethylenically unsaturated carboxylic acids or their
anhydrides can be any of the ethylenically unsaturated carboxylic
acids or their anhydrides disclosed hereinabove for making the
molybdated succinimide complex employing the succinimide of Formula
V. A preferred ethylenically unsaturated carboxylic acid or
anhydride thereof is maleic anhydride or a derivative thereof.
[0069] Generally, the ethylenically unsaturated carboxylic acid or
anhydride thereof is heated to a molten condition at a temperature
in the range of from about 50.degree. C. to about 100.degree. C.
and is thereafter mixed with the succinimide of Formula VII.
[0070] The molybdenum compounds used to prepare the molybdated
succinimide complex can be any of the molybdenum compounds
disclosed herein above for making the molybdated succinimide
complex employing the succinimide of Formula V. Particularly
preferred is molybdenum trioxide.
[0071] In step (b), a mixture of, the succinimide product of step
(a) and acidic molybdenum compound is prepared with or without a
diluent. A diluent is used, if necessary, to provide a suitable
viscosity for easy stirring. Suitable diluents are lubricating oils
and liquid compounds containing only carbon and hydrogen. If
desired, ammonium hydroxide may also be added to the reaction
mixture to provide a solution of ammonium molybdate
[0072] Generally, the reaction mixture is heated at a temperature
less than or equal to about 100.degree. C. and preferably from
about 80.degree. C. to about 100.degree. C. until the molybdenum is
sufficiently reacted. The reaction time for this step is typically
in the range of about 15 minutes to about 5 hours and preferably
about 1 to about 2 hours. The molar ratio of the molybdenum
compound to the succinimide product of step (a) is about 0.1:1 to
about 2:1, preferably from about 0.5:1 to about 1.5:1 and most
preferably about 1:1. Any water present following the reaction of
the molybdenum compound and succinimide product of step (a) can be
removed by heating the reaction mixture to a temperature greater
than about 100.degree. C., and preferably from about 120.degree. C.
to about 160.degree. C.
[0073] The lubricating oil compositions of the present invention
will contain at least about 1100 ppm of molybdenum, based upon the
total mass of the composition, provided from the one or more
oil-soluble or dispersed oil-stable molybdenum-containing
compounds. In one embodiment, the lubricating oil compositions of
the present invention will contain about 1100 ppm to about 2000 ppm
of molybdenum, based upon the total mass of the composition,
provided from the one or more oil-soluble or dispersed oil-stable
molybdenum-containing compounds.
[0074] In one embodiment, the oil-soluble or dispersed oil-stable
molybdenum-containing compound will be present in the lubricating
oil composition of the present invention such that the lubricating
oil composition has a ratio of sulfur to molybdenum of less than or
equal to about 4:1. In another embodiment, the lubricating oil
composition has a ratio of sulfur to molybdenum of less than about
3:1. In yet another embodiment, the lubricating oil composition has
a ratio of sulfur to molybdenum of about 0.5:1 to about 4:1. In
another embodiment, the lubricating oil composition has a ratio of
sulfur to molybdenum of about 1:1 to about 4:1. In still another
embodiment, the lubricating oil composition has a ratio of sulfur
to molybdenum of about 1:1 to about 3:1. In still yet another
embodiment, the lubricating oil composition has a ratio of sulfur
to molybdenum of about 1:1 to about 2.5:1.
[0075] The lubricating oil compositions of the present invention
will have a sulfur content of up to about 0.4 wt. % and preferably
up to about 0.3 wt. %. The sulfur content can be derived from
elemental sulfur or a sulfur-containing compound. The sulfur or
sulfur-containing compound may be intentionally added to the
lubricating oil composition, or it may be present in the base oil
or in one or more of the additives for the lubricating oil
composition. In one embodiment, a major amount of the sulfur in the
lubricating oil composition is derived from an active sulfur
compound, i.e., an amount greater than 50%. By "active sulfur" is
meant a sulfur compound which is antiwear active and preferably
anticorrosive. The sulfur-containing compound may be an inorganic
sulfur compound or an organic sulfur compound. The
sulfur-containing compound may be a compound containing one or more
of the groups: sulfamoyl, sulfenamoyl, sulfeno, sulfido,
sulfinamoyl, sulfino, sulfonyl, sulfo, sulfonio, sulfonyl,
sulfonyldioxy, sulfate, thio, thiocarbamoyl, thiocarbonyl,
thiocarbonylamino, thiocarboxy, thiocyanato, thioformyl, thioxo,
thioketone, thioaldehyde, thioester, and the like. The sulfur may
also be present in a hetero group or compound which contains carbon
atoms and sulfur atoms (and, optionally, other hetero atoms such as
oxygen or nitrogen) in a chain or ring. Preferred sulfur-containing
compounds include dihydrocarbyl sulfides and polysulfides such as
alkyl or alkenyl sulfides and polysulfides, sulfurized fatty acids
or esters thereof, ashless dithiophosphates, cyclic organo-sulfur
compounds, polyisobutyl thiothione compounds, ashless
dithiocarbamates and mixtures thereof.
[0076] Examples of the dihydrocarbyl sulfides or polysulfides
include compounds represented by Formula VIII:
R.sup.9--S.sub.b--R.sup.10 (VIII)
wherein R.sup.9 and R.sup.10 are the same or different and
represent a C.sub.1 to C.sub.10 alkyl group, alkenyl group or a
cyclic alkyl group, a C.sub.6 to C.sub.20 aryl group, a C.sub.7 to
C.sub.20 alkyl aryl group, or a C.sub.7 to C.sub.20 aryl alkyl
group; and b is an integer of 1 to 7. When each of R.sup.9 and
R.sup.10 is an alkyl group, the compound is called an alkyl
sulfide. Examples of the group represented by R.sup.9 and R.sup.10
in Formula VIII include methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl groups, hexyl
groups, heptyl groups, octyl groups, nonyl groups, decyl groups,
dodecyl groups, cyclohexyl, phenyl, naphthyl, tolyl, xylyl, benzyl,
and phenethyl.
[0077] One method of preparing the aromatic and alkyl sulfides
includes the condensation of a chlorinated hydrocarbon with an
inorganic sulfide whereby the chlorine atom from each of two
molecules is displaced, and the free valence from each molecule is
joined to a divalent sulfur atom. Generally, the reaction is
conducted in the presence of elemental sulfur.
[0078] Examples of alkenyl sulfides are described, for example, in
U.S. Pat. No. 2,446,072. These sulfides can be prepared by
interacting an olefinic hydrocarbon containing from 3 to 12 carbon
atoms with elemental sulfur in the presence of zinc or a similar
metal generally in the form of an acid salt. Representative
examples of alkenyl sulfides include
6,6'-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfide and
disulfide, 2-methyl-2-butenyl monosulfide and disulfide and the
like.
[0079] The sulfurized fatty acid or ester thereof can be prepared
by reacting, for example, sulfur, sulfur monochloride, and/or
sulfur dichloride with an unsaturated fatty acid or ester thereof
under elevated temperatures. Suitable fatty acids include C.sub.8
to C.sub.24 unsaturated fatty acids such as, for example,
palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid,
vaccenic acid, linoleic acid, linolenic acid, oleostearic acid,
licanic acid, paranaric acid, tariric acid, gadoleic acid,
arachidonic acid, cetoleic acid and the like. Also useful are mixed
unsaturated fatty acid, such as animal fats and vegetable oils,
e.g., tall oil, linseed oil, olive oil, castor oil, peanut oil,
rape oil, fish oil, sperm oil, and the like. Suitable fatty acid
esters include C.sub.1 to C.sub.20 alkyl esters of the foregoing
fatty acids. Exemplary fatty esters include lauryl tallate, methyl
oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate,
lauryl ricinoleate, oleyl linoleate, oleyl stearate, alkyl
glycerides and the like.
[0080] One class of suitable ashless dithiophosphates for use
herein include those of the Formula IX:
##STR00009##
wherein R.sup.11 and R.sup.12 are independently an alkyl group
having 3 to 8 carbon atoms (commercially available as VANLUBE.RTM.
7611M, from R.T. Vanderbilt Co., Inc.).
[0081] Another class of suitable ashless dithiophosphates for use
herein include dithiophosphoric acid esters of carboxylic acid such
as those commercially available as IRGALUBE.RTM. 63 from Ciba Geigy
Corp.
[0082] Yet another class of suitable ashless dithiophosphates for
use herein include triphenylphosphorothionates such as those
commercially available as IRGALUBE.RTM. TPPT from Ciba Geigy
Corp.
[0083] Suitable polyisobutyl thiothione compounds include those
compounds represented by Formula X:
##STR00010##
wherein R.sup.13 is hydrogen or methyl; X is sulfur or oxygen; m is
an integer from 1 to 9; and n is 0 or 1, and when n is 0 then
R.sup.13 is methyl, and when n is 1 then R.sup.13 is hydrogen.
Examples of these polyisobutyl thiothione compounds are disclosed,
in, for example, U.S. Patent Application Publication No.
20050153850, the contents of which are incorporated by reference
herein.
[0084] In a preferred embodiment, a sulfur compound for use in the
lubricating oil composition of the present invention is a
bisdithiocarbamate compound of Formula XI:
##STR00011##
wherein R.sup.13, R.sup.14, R.sup.15, and R.sup.16 are the same or
different and are aliphatic hydrocarbyl groups having 1 to 13
carbon atoms and R.sup.17 is an alkylene group having 1 to 8 carbon
atoms. The bisdithiocarbamates of Formula XI are known compounds
and described in U.S. Pat. No. 4,648,985 incorporated herein by
reference. The aliphatic hydrocarbyl groups having 1 to 13 carbon
atoms can be branched or straight chain alkyl groups having 1 to 13
carbon atoms. A preferred bisdithiocarbamate compound for use
herein is methylenebis(dibutyldithiocarbamate) available
commercially under the trademark Vanlube.degree. 7723 (R. T.
Vanderbilt Co., Inc.).
[0085] The lubricating oil compositions of the present invention
can be substantially free of any phosphorus content. In one
embodiment, the lubricating oil compositions of the present
invention are substantially free of any zinc dialkyl
dithiophosphate.
[0086] The lubricating oil compositions of the present invention
may also contain other conventional additives for imparting
auxiliary functions to give a finished lubricating oil composition
in which these additives are dispersed or dissolved. For example,
the lubricating oil compositions can be blended with antioxidants,
anti-wear agents, detergents such as metal detergents, rust
inhibitors, dehazing agents, demulsifying agents, metal
deactivating agents, friction modifiers, pour point depressants,
antifoaming agents, co-solvents, package compatibilisers,
corrosion-inhibitors, ashless dispersants, dyes, extreme pressure
agents, and the like and mixtures thereof. A variety of the
additives are known and commercially available. These additives, or
their analogous compounds, can be employed for the preparation of
the lubricating oil compositions of the invention by the usual
blending procedures.
[0087] Examples of antioxidants include, but are not limited to,
aminic types, e.g., diphenylamine, phenyl-alpha-napthyl-amine,
N,N-di(alkylphenyl)amines; and alkylated phenylene-diamines;
phenolics such as, for example, BHT, sterically hindered alkyl
phenols such as 2,6-di-tert-butylphenol,
2,6-di-tert-butyl-p-cresol, and
2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; and mixtures
thereof.
[0088] Examples of ashless dispersants include, but are not limited
to, polyalkylene succinic anhydrides; non-nitrogen containing
derivatives of a polyalkylene succinic anhydride; a basic nitrogen
compound selected from the group consisting of succinimides,
carboxylic acid amides, hydrocarbyl monoamines, hydrocarbyl
polyamines, Mannich bases, phosphonoamides, and phosphoramides;
triazoles, e.g., alkyltriazoles and benzotriazoles; copolymers
which contain a carboxylate ester with one or more additional polar
function, including amine, amide, imine, imide, hydroxyl, carboxyl,
and the like, e.g., products prepared by copolymerization of long
chain alkyl acrylates or methacrylates with monomers of the above
function, and the like and mixtures thereof.
[0089] Examples of rust inhibitors include, but are not limited to,
nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl
ether, polyoxyethylene higher alcohol ether, polyoxyethylene
nonylphenyl ether, polyoxyethylene octylphenyl ether,
polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether,
polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol
monooleate, and polyethylene glycol monooleate; stearic acid and
other fatty acids; dicarboxylic acids; metal soaps; fatty acid
amine salts; metal salts of heavy sulfonic acid; partial carboxylic
acid ester of polyhydric alcohol; phosphoric esters; (short-chain)
alkenyl succinic acids; partial esters thereof and
nitrogen-containing derivatives thereof; synthetic
alkarylsulfonates, e.g., metal dinonylnaphthalene sulfonates; and
the like and mixtures thereof.
[0090] Examples of friction modifiers include, but are not limited
to, alkoxylated fatty amines; fatty phosphites, fatty epoxides,
fatty amines, metal salts of fatty acids, fatty acid amides,
glycerol esters, and fatty imidazolines as disclosed in U.S. Pat.
No. 6,372,696, the contents of which are incorporated by reference
herein; friction modifiers obtained from a reaction product of a
C.sub.4 to C.sub.75, preferably a C.sub.6 to C.sub.24, and most
preferably a C.sub.6 to C.sub.20 fatty acid ester and a
nitrogen-containing compound selected from the group consisting of
ammonia, and an alkanolamine, and the like and mixtures
thereof.
[0091] Examples of antifoaming agents include, but are not limited
to, polymers of alkyl methacrylate; polymers of dimethylsilicone,
and the like and mixtures thereof.
[0092] Each of the foregoing additives, when used, is, used at a
functionally effective amount to, impart the desired properties to
the lubricant. Thus, for example, if an additive is a friction
modifier, a functionally effective amount of this friction modifier
would be an amount sufficient to impart the desired friction
modifying characteristics to the lubricant. Generally, the
concentration of each of these additives, when used, ranges from
about 0.001% to about 20% by weight, and in one embodiment about
0.01% to about 10% by weight based on the total weight of the
lubricating oil composition.
[0093] The final application of the lubricating oil compositions of
this invention may be, for example, in marine cylinder lubricants
in crosshead diesel engines, crankcase lubricants in automobiles
and railroads and the like, lubricants for heavy machinery such as
steel mills and the like, or as greases for bearings and the like.
In one embodiment, the lubricating oil compositions of this
invention are used to lubricate a diesel engine such as a heavy
duty diesel engine or a compression ignited diesel engine equipped
with at least one of an exhaust gas recirculation (EGR) system; a
catalytic converter; and a particulate trap.
[0094] Whether the lubricating oil composition is fluid or solid
will ordinarily depend on whether a thickening agent is present.
Typical thickening agents include polyurea acetates, lithium
stearate, and the like.
[0095] The following non-limiting examples are illustrative of the
present invention.
EXAMPLE 1
[0096] A lubricating oil composition was prepared by blending
together the following components to obtain a SAE 15W-40 viscosity
grade formulation:
[0097] (1) 2300 ppm, in terms of sulfur content, of a combination
of a methylene bis di-n-butyl dithiocarbamate (0.7 wt. % in the
finished oil) and one or more detergents, wherein 1900 ppm of
sulfur is derived from active sulfur (i.e., methylene bis
di-n-butyl dithiocarbamate) and 400 ppm of sulfur is derived from
nonactive sulfur compound (i.e., the detergent).
[0098] (2) 400 ppm, in terms of boron content, of a combination of
a borated dispersant (5.2 wt % in the finished oil) and borated
sulfonate (3 mmol/kg in the finished oil) having a total, base
number (TBN) of 160.
[0099] (3) 1200 ppm, in terms of molybdenum content, of a
molybdenum succinimide complex.
[0100] (4) 2.6 wt. % of a dispersant.
[0101] (5) 1 wt. % of a diphenylamine antioxidant.
[0102] (6) 1 wt. % of a hindered phenol antioxidant.
[0103] (7) 0.3 wt. % of a pour point depressant.
[0104] (8) 6.6 wt. % of a dispersant viscosity index improver.
[0105] (9) 10 ppm, in terms of silicon content, of a foam
inhibitor.
[0106] The remainder was diluent oil composed of approximately 72
wt. % of a CHEVRON 220N Group II base oil and approximately 28 wt.
% of a CHEVRON 600N Group II base oil.
[0107] The resulting lubricating oil composition had a sulfated ash
content of 0.3 wt. % as determined by ASTM D874.
COMPARATIVE EXAMPLE A
[0108] A lubricating oil composition was prepared by blending
together the following components to obtain a SAE 15W-40 viscosity
grade formulation:
[0109] (1) 400 ppm, in terms of sulfur content, of a nonactive
sulfur compound (i.e., a detergent).
[0110] (2) 400 ppm, in terms of boron content, of a combination of
a borated dispersant (5.2 wt % in the finished oil) and borated
sulfonate (3 mmol/kg in the finished oil) having a total base
number (TBN) of 160.
[0111] (3) 90 ppm, in terms of molybdenum content, of a molybdenum
succinimide complex.
[0112] (4) 2.6 wt. % of a dispersant.
[0113] (5) 1 wt. % of a diphenylamine antioxidant.
[0114] (6) 1 wt. % of a hindered phenol antioxidant.
[0115] (7) 0.3 wt. % of a pour point depressant.
[0116] (8) 6.6 wt. % of a dispersant viscosity index improver.
[0117] (9) 10 ppm, in terms of silicon content, of a foam
inhibitor.
[0118] (10) The remainder was diluent oil composed of approximately
82 wt. % of a CHEVRON 220N Group II base oil and approximately 18
wt. % of a CHEVRON 600N Group II base oil.
[0119] The resulting lubricating oil composition had a sulfated ash
content of 0.2 wt. % as determined by ASTM D874.
COMPARATIVE EXAMPLE B
[0120] A lubricating oil composition was prepared by blending
together the following components to obtain a SAE 15W-40 viscosity
grade formulation:
[0121] (1) 400 ppm, in terms of sulfur content, of a nonactive
sulfur compound (i.e., a detergent).
[0122] (2) 750 ppm, in terms of boron content, of a combination of
a borated dispersant (5.2 wt % in the finished oil), borated
calcium sulfonate (3 mmol/kg Ca basis in the finished oil) having a
TBN of 160, and a dispersed hydrated sodium borate (0.5 wt. % in
the finished oil).
[0123] (3) 90 ppm, in terms of molybdenum content, of a molybdenum
succinimide complex.
[0124] (4) 2.6 wt. % of a dispersant.
[0125] (5) 1 wt. % of a diphenylamine antioxidant.
[0126] (6) 1 wt. % of a hindered phenol antioxidant.
[0127] (7) 0.5 wt. % of a pour point depressant.
[0128] (8) 4.1 wt. % of a dispersant viscosity index improver.
[0129] (9) 10 ppm, in terms of silicon content, of a foam
inhibitor.
[0130] (10) The remainder was diluent oil composed of approximately
55 wt. % of a Group III base oil and approximately 45 wt. % of a
Group II base oil.
[0131] The resulting lubricating oil composition had a sulfated ash
content of 0:4 wt. % as determined by ASTM D874.
COMPARATIVE EXAMPLE C
[0132] A lubricating oil composition was prepared by blending
together the following components to obtain a SAE 15W-40 viscosity
grade formulation:
[0133] (1) 2300 ppm, in terms of sulfur content, of a combination
of a methylene bis di-n-butyl dithiocarbamate (0.7 wt. % in the
finished oil) and one or more detergents, wherein 1900 ppm of
sulfur is derived from active sulfur (i.e., methylene bis
di-n-butyl dithiocarbamate) and 400 ppm of sulfur is derived from
nonactive sulfur compound (i.e., the detergent).
[0134] (2) 750 ppm, in terms of boron content, of a combination of
a borated dispersant (5.2 wt. % in the finished oil), borated
calcium sulfonate (3 mmol/kg Ca basis in the finished oil) having a
TBN of 160, and a dispersed hydrated sodium borate (0.5 wt. % in
the finished oil).
[0135] (3) 90 ppm, in terms of molybdenum content, of a molybdenum
succinimide complex.
[0136] (4) 2.6 wt. % of a dispersant.
[0137] (5) 1 wt. % of a diphenylamine antioxidant.
[0138] (6) 1 wt. % of a hindered phenol antioxidant.
[0139] (7) 0.5 wt. % of a pour point depressant.
[0140] (8) 6.7 wt. % of a dispersant viscosity index improver.
[0141] (9) 10 ppm, in terms of silicon content, of a foam
inhibitor.
[0142] (10) The remainder was diluent oil composed of approximately
72 wt. % of a CHEVRON 220N Group II base oil and approximately 28
wt. % of a CHEVRON 600N Group II base oil.
[0143] The resulting lubricating oil composition had a sulfated ash
content of 0.4 wt. % as determined by ASTM D874.
[0144] Testing
[0145] API CJ-4 Cummins ISM Test
[0146] The lubricating oil compositions of Example 1 and
Comparative Examples A-C were evaluated for their wear performance.
A screener version of the CJ-4 Cummins engine test was used to
determine heavy duty diesel valve train wear performance by
measuring the injector adjusting screw weight loss (IASWL). The
CJ-4 Cummins Test is a Cummins ISM engine equipped with EGR. The
engine test duration is 100 hours. The results for this test are
set forth below in Table 1.
TABLE-US-00001 TABLE 1 IASWL Example 1 5.9 Comp. Ex. A 22.3 Comp.
Ex. B 31.2 Comp. Ex. C 38.6
As the data show, the lubricating oil composition of Example 1
significantly reduced the injector screw wear as compared to the
lubricating oil compositions of Comparative Examples A-C. Thus, it
is believed that the lubricating oil composition of the present
invention is capable of providing a surface film on the injector
screw that will be sufficient to provide improved wear
benefits.
[0147] It will be understood that various modifications may be made
to the embodiments disclosed herein. Therefore the above
description should not be construed as limiting, but merely as
exemplifications of preferred embodiments. For example, the
functions described above and implemented as the best mode for
operating the present invention are for illustration purposes only.
Other arrangements and methods may be implemented by those skilled
in the art without departing from the scope and spirit of this
invention. Moreover, those skilled in the art will envision other
modifications within the scope and spirit of the claims appended
hereto.
* * * * *