U.S. patent application number 17/022817 was filed with the patent office on 2021-03-25 for lubricant composition.
The applicant listed for this patent is BASF SE. Invention is credited to Thomas E. Hayden, Michael Hoey, Eugene Scanlon, Marinus Vaarkamp.
Application Number | 20210087489 17/022817 |
Document ID | / |
Family ID | 1000005240474 |
Filed Date | 2021-03-25 |
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United States Patent
Application |
20210087489 |
Kind Code |
A1 |
Hoey; Michael ; et
al. |
March 25, 2021 |
LUBRICANT COMPOSITION
Abstract
Disclosed herein is a process for lubricating an internal
combustion engine with a lubricant composition that may be
substantially ash free. The ashless lubricant composition described
herein may comprise primary antioxidants, such as aminic diphenyl
amines, alkylated phenyl-naphthyl amines, and phenolic
antioxidants. The ashless lubricant composition described herein
may also comprise sulfur containing products that may work as
secondary antioxidants. Other components such as ashless antiwear
components, dispersants, pour point depressants, friction
modifiers, and metal deactivators may also be used to formulate an
ashless lubricant composition according to an embodiment.
Inventors: |
Hoey; Michael; (Tarrytown,
NY) ; Hayden; Thomas E.; (Tarrytown, NY) ;
Scanlon; Eugene; (Tarrytown, NY) ; Vaarkamp;
Marinus; (Tarrytown, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Family ID: |
1000005240474 |
Appl. No.: |
17/022817 |
Filed: |
September 16, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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62902695 |
Sep 19, 2019 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2215/065 20130101;
C10M 151/02 20130101; C10N 2030/10 20130101; C10M 2207/026
20130101; C10M 141/08 20130101; C10M 133/12 20130101; C10M 2215/064
20130101; C10N 2040/25 20130101; C10M 151/04 20130101 |
International
Class: |
C10M 133/12 20060101
C10M133/12; C10M 151/02 20060101 C10M151/02; C10M 151/04 20060101
C10M151/04 |
Claims
1. A process for lubricating an internal combustion engine, the
process comprising adding a lubricant composition to an internal
combustion engine, wherein the lubricant composition comprises: a
base oil, one or more antioxidants selected from the group
consisting of alkylated phenyl-naphthyl amines antioxidants,
diphenylamine antioxidants, phenolic antioxidants, and combinations
thereof, and one or more sulfur-containing additives.
2. The process of claim 1, wherein the one or more antioxidants, in
total, are present from about 0.2 wt % to about 10.0 wt %, based on
the total weight of the lubricant composition.
3. The process of any one of the preceding claims, wherein a sulfur
concentration provided by the one or more sulfur-containing
additives, in total, ranges from about 75 ppm to about 1000 ppm by
weight, based on the total weight of the lubricant composition.
4. The process of any one of the preceding claims, wherein the one
or more antioxidants comprises N-.alpha.-naphthyl-N-phenylamine
antioxidants of formula ##STR00011## wherein R is H,
C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18
alkynyl, --C(O)C.sub.1-C.sub.18 alkyl or --C(O)aryl and R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are each independently H,
C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18
alkylamino, C.sub.1-C.sub.18 dialkylamino, C.sub.1-C.sub.18
alkylthio, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl or
C.sub.7-C.sub.21 aralkyl.
5. The process of any one of the preceding claims, wherein the one
or more antioxidants comprises diphenylamine antioxidants of
formula ##STR00012## wherein R is H, C.sub.1-C.sub.18 alkyl,
C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl,
--C(O)C.sub.1-C.sub.18 alkyl or --C(O)aryl and R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are each independently H, C.sub.1-C.sub.18
alkyl, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkylamino,
C.sub.1-C.sub.18 dialkylamino, C.sub.1-C.sub.18 alkylthio,
C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl or
C.sub.7-C.sub.21 aralkyl.
6. The process of claim 4, wherein the
N-.alpha.-naphthyl-N-phenylamine antioxidants are of formula
##STR00013## wherein R.sub.1 and R.sub.2 are each independently H
or C.sub.1-C.sub.18 alkyl.
7. The process of claim 6, wherein R.sub.2 is H and R.sub.1 is
t-butyl, t-octyl or branched nonyl.
8. The process of claim 5, wherein the diphenylamine antioxidants
are of formula ##STR00014## wherein R.sub.1 and R.sub.2 are each
independently H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl
or C.sub.7-C.sub.21 aralkyl.
9. The process of claim 8, wherein R.sub.1 and R.sub.2 are each
independently H, tert-butyl, tert-octyl or branched nonyl.
10. The process of any one of the preceding claims, wherein the
lubricant composition comprises sulfur-containing additives
selected from a group consisting of sulfur-containing hindered
phenolic compounds, sulfur-containing rust inhibitors,
sulfur-containing friction modifiers and sulfur-containing antiwear
additives.
11. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more sulfur-containing
additives selected from a group consisting of
2,4-di-octylthiomethyl-6-tert-butylphenol,
2,4-di-octylthiomethyl-6-methylphenol,
2,4-di-octylthiomethyl-6-ethylphenol or
2,6-di-dodecylthiomethyl-4-nonylphenol,
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis-(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide, octadecyl
4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl
4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl
3,5-di-tert-butyl-4-hydroxy-benzylmercaptoacetate and esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid,
3,5-di-tert-butyl-4-hydroxyphenylacetic acid or
.beta.-(5-tert-butyl-4-hydroxyphenyl)-3-thiabutyric acid with
thiodiethylene glycol, 3-thiaundecanol or thiapentadecanol.
12. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more sulfur-containing
additives selected from a group consisting of organomolybdenum
dithiocarbamates, organomolybdenum dithiophosphates and
organomolybdenum compounds based on dispersants and molybdenum
disulfide.
13. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more sulfur-containing
additives selected from a group consisting of sulfurized olefins,
sulfurized vegetable oils, dialkyldithiophosphate esters, zinc
dialkyldithiophosphates, alkyl or aryl di- or tri-sulfides,
derivatives of 2,5-dimercapto-1,3,4-thiadiazole,
ethyl(bisisopropyloxyphosphinothioyl)-thiopropionate, triphenyl
thiophosphate, tris(alkylphenyl) phosphorothioates,
diphenylmonononylphenyl phosphorothioate, isobutylphenyl diphenyl
phosphorothioate, a dodecylamine salt of
3-hydroxy-1,3-thiaphosphetan 3-oxide, trithiophosphoric acid
5,5,5-tris-isooctyl 2-acetate, derivatives of
2-mercaptobenzothiazole, ethoxycarbonyl 5-octyldithiocarbamate and
dihydrocarbyl dithiophosphate metal salts.
14. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more sulfur-containing
additives selected from a group consisting of sulfurized
olefins.
15. The process of claim 14, wherein the sulfurized olefins
comprise sulfurized isobutylene.
16. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more sulfur-containing
additives selected from a group consisting of di-tert-alkyl
polysulfides.
17. The process of claim 16, wherein the di-tert-alkyl polysulfides
are selected from a group consisting of di-tert-butyl polysulfide,
di-tert-dodecyl polysulfide and di-tert-nonyl polysulfide.
18. The process of any one of the preceding claims, wherein the
lubricant composition comprises a base oil selected from a group
consisting of Group II, Group III and Group IV base oils.
19. The process of any one of the preceding claims, wherein the
lubricant composition comprises a base oil selected from a group
consisting of polyalphaolefins.
20. The process of any one of the preceding claims, wherein the
lubricant composition comprises a base oil selected from a group
consisting of synthetic esters.
21. The process of any one of the preceding claims, wherein the
lubricant composition comprises a base oil that comprises one or
more polyalkylene glycols.
22. The process of any one of the preceding claims, wherein the
lubricant composition comprises one or more
N-.alpha.-naphthyl-N-phenylamine antioxidants and one or more
diphenylamine antioxidants and wherein a weight/weight ratio of
N-.alpha.-naphthyl-N-phenylamine antioxidants to diphenylamine
antioxidants is from about 1/9 to about 9/1.
23. The process of any one of the preceding claims, wherein the
lubricant composition comprises a base oil is an amount of from
about 80 wt % to about 99.7 wt %, based on the total weight of the
lubricant composition.
24. The process of any one of the preceding claims, wherein the
lubricant composition comprises less than 0.1 wt % of zinc
dialkyldithiophosphate salts, based on the total weight of the
lubricant composition.
25. The process of claim 24, wherein the lubricant composition is
substantially free of zinc dialkyldithiophosphate salts.
26. The process of any one of claims 24-25, wherein the zinc
dialkyldithiophosphate salts delivers less than about 500 ppm
phosphorus by weight, based on the total weight of the lubricant
composition.
27. The process of claim 26, wherein the zinc
dialkyldithiophosphate salts delivers less than about 300 ppm
phosphorus by weight, based on the total weight of the lubricant
composition.
28. The process according to any one of the preceding claims,
wherein a sulfur concentration provided by the one or more
sulfur-containing additives, in total, ranges from about 50 ppm to
about 1000 ppm by weight, based on the total weight of the
lubricant composition.
29. The process according to any one of the preceding claims,
wherein the lubricant composition comprises less than about 0.1 wt
% overbased calcium, magnesium, salts of alkyl aromatic sulfonates,
phenates, or salicylates, independently or in total, based on the
total weight of the lubricant composition.
30. The process according to any one of the preceding claims,
wherein the lubricant composition further comprises an ashless
antiwear components, dispersants, pour point depressants, friction
modifiers, and metal deactivators.
31. The process of claim 30, wherein the ashless antiwear
components comprise a phosphorus derivative.
32. The process of any one of claims 30-31, wherein the ashless
antiwear components are present from about 0.5 wt % to about 10.0
wt %, based on the total weight of the lubricant composition.
33. The process of any one of claims 30-32, wherein the dispersants
are present from about 0.5 wt % to about 5.0 wt %, based on the
total weight of the lubricant composition.
34. The process of any one of claims 30-33, wherein the pour point
depressants are present from about 0.05 wt % to about 0.2 wt %,
based on the total weight of the lubricant composition.
35. The process of any one of claims 30-34, wherein the friction
modifiers are present from about 0.2 wt % to about 0.9 wt %, based
on the total weight of the lubricant composition.
36. The process of any one of claims 30-35, wherein the metal
deactivators are present from about 0.1 wt % to about 0.9 wt %,
based on the total weight of the lubricant composition.
37. A system comprising an internal combustion engine and an
ashless lubricant composition, wherein the ashless lubricant
composition comprises: a base oil, one or more antioxidants
selected from the group consisting of alkylated phenyl-naphthyl
amines antioxidants, diphenylamine antioxidants, phenolic
antioxidants, and combinations thereof, and one or more
sulfur-containing additives.
Description
FIELD OF THE INVENTION
[0001] This disclosure relates to formulated ashless lubricant
compositions, methods for using said ashless lubricant compositions
in internal combustion engines, and to internal combustion engine
systems operating with the lubricant compositions described
herein.
BACKGROUND OF THE INVENTION
[0002] Engine oils are utilized to lubricate internal combustion
engines, but the ash that they contain can damage a car's catalytic
converter. To prevent this, cars use a simple trap to isolate any
particles from the exhaust and contain the ash that they contain.
Ash has also been found to initiate a destructive condition in
Gasoline Direct Injected engines that is called Low Speed
Pre-Ignition (LSPI).
OBJECTS AND SUMMARY OF THE INVENTION
[0003] In certain embodiments, disclosed is a process for
lubricating an internal combustion engine. The process may comprise
adding a lubricant composition to an internal combustion engine.
The lubricant composition may comprise a base oil, one or more
antioxidants selected from the group consisting of alkylated
phenyl-naphthyl amine antioxidants, diphenylamine antioxidants,
phenolic antioxidants, and combinations thereof, and one or more
sulfur-containing additives. The lubricant composition may be
ashless.
[0004] In certain embodiments, disclosed is a process comprising
running an internal combustion engine with a lubricant composition.
The lubricant composition may be ashless and may comprise a base
oil, one or more antioxidants selected from the group consisting of
alkylated phenyl-naphthyl amine antioxidants, diphenylamine
antioxidants, phenolic antioxidants, and combinations thereof, and
one or more sulfur-containing additives.
[0005] In certain embodiments, disclosed is a system comprising an
internal combustion engine and an ashless lubricant composition.
The ashless lubricant composition may comprise a base oil, one or
more antioxidants selected from the group consisting of alkylated
phenyl-naphthyl amine antioxidants, diphenylamine antioxidants,
phenolic antioxidants, and combinations thereof, and one or more
sulfur-containing additives.
DETAILED DESCRIPTION
[0006] Engine oils are utilized to lubricate internal combustion
engines, but the ash that they contain can damage a car's catalytic
converter. Ash has also been found to initiate a destructive
condition in Gasoline Direct Injected engines that is called Low
Speed Pre-Ignition (LSPI). Accordingly, disclosed herein are
ashless lubricant compositions that may be utilized to lubricate
internal combustion engines. In certain embodiments, a suitable
lubricant composition is an ashless internal combustion engine
lubricant. Suitable ashless lubricant compositions may comprise,
among other optional components, a base oil as well as primary and
secondary antioxidants.
[0007] The term "ashless" as used herein may indicate that the
lubricant composition comprises less than about 0.5 wt %, less than
about 0.4 wt %, less than about 0.3 wt %, less than about 0.2 wt %,
less than about 0.1 wt %, less than about 0.05 wt %, less than
about 0.01 wt %, less than about 0.001 wt %, less than about 0.0001
wt %, or no (i.e. 0 wt %) overbased calcium, magnesium, salts of
alkyl aromatic sulfonates, phenates, or salicylates, calculated for
each component independently or in total, based on the total weight
of the lubricant composition.
[0008] The base oil, or lubricating base oil or base stock, may be
the largest component by weight of a finished fully formulated
lubricating composition.
[0009] Lubricating base oils that may be useful in the present
disclosure are both natural oils and synthetic oils as well as
non-conventional oils (or mixtures thereof) which can be used
unrefined, refined, or re-refined (the latter is also known as
reclaimed or reprocessed oil). Unrefined oils are those obtained
directly from a natural or synthetic source and used without added
purification. These include shale oil obtained directly from
retorting operations, petroleum oil obtained directly from primary
distillation and ester oil obtained directly from an esterification
process. Refined oils are similar to the oils discussed for
unrefined oils except refined oils are subjected to one or more
purification steps to improve at least one lubricating oil
property. One skilled in the art is familiar with many purification
processes. These processes include solvent extraction, secondary
distillation, acid extraction, base extraction, filtration and
percolation. Re-refined oils are obtained by processes analogous to
refined oils but using an oil that has been previously used as a
feed stock.
[0010] Groups I, II, III, IV and V are broad base oil stock
categories developed and defined by the American Petroleum
Institute (API Publication 1509; www.API.org) to create guidelines
for lubricant base oils. Group I base stocks have a viscosity index
of from 80 to 120 and contain greater than 0.03% sulfur and/or less
than 90% saturates. Group II base stocks have a viscosity index of
from 80 to 120, and contain less than or equal to 0.03% sulfur, and
greater than or equal to 90% saturates. Group III base stocks have
a viscosity index greater than 120 and contain less than or equal
to 0.03% sulfur and greater than 90% saturates. Group IV includes
polyalphaolefins (PAO). Group V base stocks includes base stocks
not included in Groups I-IV. The table below summarizes properties
of each of these five groups.
TABLE-US-00001 Saturates Sulfur Viscosity Index Group I <90
>0.03% .gtoreq.80 and <120 Group II .gtoreq.90 .ltoreq.0.03%
.gtoreq.80 and <120 Group III .gtoreq.90 .ltoreq.0.03%
.gtoreq.120 Group IV ---- polyalphaolefins (PAO) ---- Group V ----
all other base stocks not of Groups I-IV ----
[0011] Natural oils include animal oils, vegetable oils (castor oil
and lard oil, for example), and mineral oils. Animal and vegetable
oils possessing favorable thermal oxidative stability can be used.
In a certain embodiment, natural oils include mineral oils. Mineral
oils vary widely as to their crude source, for example, as to
whether they are paraffinic, naphthenic, or mixed
paraffinic-naphthenic. Oils derived from coal or shale are also
useful. Natural oils vary also as to the method used for their
production and purification, for example, their distillation range
and whether they are straight run or cracked, hydrorefined, or
solvent extracted.
[0012] Group II and/or Group III hydroprocessed or hydrocracked
base stocks, including synthetic oils such as polyalphaolefins,
alkyl aromatics and synthetic esters are also well known base stock
oils.
[0013] Synthetic oils include hydrocarbon oil. Hydrocarbon oils
include oils such as polymerized and interpolymerized olefins
(polybutylenes, polypropylenes, propylene isobutylene copolymers,
ethylene-olefin copolymers, and ethylene-alphaolefin copolymers,
for example). Polyalphaolefin (PAO) oil base stocks are commonly
used synthetic hydrocarbon oil. By way of example, PAOs derived
from C.sub.6, C.sub.8, C.sub.10, C.sub.12, C.sub.14 olefins or
mixtures thereof may be utilized. See U.S. Pat. Nos. 4,956,122;
4,827,064; and 4,827,073.
[0014] The number average molecular weights of the PAOs, which are
known materials and generally available on a major commercial scale
from suppliers such as ExxonMobil Chemical Company, Chevron
Phillips Chemical Company, BP, and others, typically vary from 250
to 3,000, although PAO's may be made in viscosities up to 100 cSt
(100.degree. C.). The PAOs may typically comprise relatively low
molecular weight hydrogenated polymers or oligomers of alphaolefins
which include, but are not limited to, C2 to C32 alphaolefins, for
example C8 to C16 alphaolefins, such as 1-hexene, 1-octene,
1-decene, 1-dodecene and the like. Polyalphaolefins may include
poly-1-hexene, poly-1-octene, poly-1-decene and poly-1-dodecene and
mixtures thereof and mixed olefin-derived polyolefins. However, the
dimers of higher olefins in the range of C14 to C18 may be used to
provide low viscosity base stocks of acceptably low volatility.
Depending on the viscosity grade and the starting oligomer, the
PAOs may be predominantly trimers and tetramers of the starting
olefins, with minor amounts of the higher oligomers, having a
viscosity range of 1.5 to 12 cSt. PAO fluids of particular use may
include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof.
Bi-modal mixtures of PAO fluids having a viscosity range of 1.5 to
about 100 cSt or to about 300 cSt may be used if desired.
[0015] The PAO fluids may be conveniently made by the
polymerization of an alphaolefin in the presence of a
polymerization catalyst such as the Friedel-Crafts catalysts
including, for example, aluminum trichloride, boron trifluoride or
complexes of boron trifluoride with water, alcohols such as
ethanol, propanol or butanol, carboxylic acids or esters such as
ethyl acetate or ethyl propionate. For example the methods
disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 may be
conveniently used herein. Other descriptions of PAO synthesis are
found in the following U.S. Pat. Nos. 3,742,082; 3,769,363;
3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355;
4,956,122; and 5,068,487. The dimers of the C14 to C18 olefins are
described in U.S. Pat. No. 4,218,330.
[0016] Other useful lubricant composition base oils include wax
isomerate base stocks and base oils, comprising hydroisomerized
waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels
hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes,
Gas-to-Liquids (GTL) base stocks and base oils, and other wax
isomerate hydroisomerized base stocks and base oils, or mixtures
thereof. Fischer-Tropsch waxes, the high boiling point residues of
Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with
very low sulfur content. The hydroprocessing used for the
production of such base stocks may use an amorphous
hydrocracking/hydroisomerization catalyst, such as one of the
specialized lube hydrocracking (LHDC) catalysts or a crystalline
hydrocracking/hydroisomerization catalyst, for example a zeolitic
catalyst. For example, one useful catalyst is ZSM-48 as described
in U.S. Pat. No. 5,075,269. Processes for making
hydrocracked/hydroisomerized distillates and
hydrocracked/hydroisomerized waxes are described, for example, in
U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as
well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and
1,390,359. Particularly favorable processes are described in
European Patent Application Nos. 464546 and 464547, also
incorporated herein by reference. Processes using Fischer-Tropsch
wax feeds are described in U.S. Pat. Nos. 4,594,172 and
4,943,672.
[0017] Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived
base oils, and other wax-derived hydroisomerized (wax isomerate)
base oils be advantageously used in the instant disclosure, and may
have useful kinematic viscosities at 100.degree. C. of 3 cSt or 3.5
cSt to 25 cSt, 30 cSt or 50 cSt, as exemplified by GTL 4 with
kinematic viscosity of 4.0 cSt at 100.degree. C. and a viscosity
index of 141. These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch
wax derived base oils, and other wax-derived hydroisomerized base
oils may have useful pour points of -20.degree. C. or lower, and
under some conditions may have advantageous pour points of
-25.degree. C. or lower, with useful pour points of -30.degree. C.
to -40.degree. C. or lower. Useful compositions of Gas-to-Liquids
(GTL) base oils, Fischer-Tropsch wax derived base oils, and
wax-derived hydroisomerized base oils are recited for example in
U.S. Pat. Nos. 6,080,301; 6,090,989 and 6,165,949.
[0018] Hydrocarbyl aromatics can be used as base oil or base oil
component and can be any hydrocarbyl molecule that contains at
least 5% of its weight derived from an aromatic moiety such as a
benzenoid moiety or naphthenoid moiety, or their derivatives. These
hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes,
alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides,
alkylated bis-phenol A, alkylated thiodiphenol, and the like. The
aromatic can be mono-alkylated, dialkylated, polyalkylated, and the
like. The aromatic can be mono- or poly-functionalized. The
hydrocarbyl groups can also be comprised of mixtures of alkyl
groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl
groups and other related hydrocarbyl groups. The hydrocarbyl groups
can range from C6 up to C60, for example from C8 to C20. A mixture
of hydrocarbyl groups may be advantageous, and up to three such
substituents may be present.
[0019] The hydrocarbyl group can optionally contain sulfur, oxygen,
and/or nitrogen containing substituents. The aromatic group can
also be derived from natural (petroleum) sources, provided at least
5% of the molecule is comprised of an above-type aromatic moiety.
Viscosities at 100.degree. C. for the hydrocarbyl aromatic
component may be from about 3 cSt or about 3.4 cSt to about 20 cSt
or about 50 cSt. In one embodiment, an alkyl naphthalene where the
alkyl group is primarily comprised of 1-hexadecene is used. Other
alkylates of aromatics can be advantageously used. Naphthalene or
methyl naphthalene, for example, can be alkylated with olefins such
as octene, decene, dodecene, tetradecene or higher, mixtures of
similar olefins, and the like. Useful concentrations of hydrocarbyl
aromatic in a lubricant oil composition can be from about 2% or
about 4% to about 15%, about 20% or about 25%, depending on the
application.
[0020] Alkylated aromatics such as the hydrocarbyl aromatics of the
present disclosure may be produced by well-known Friedel-Crafts
alkylation of aromatic compounds. See Friedel-Crafts and Related
Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York,
1963. For example, an aromatic compound, such as benzene or
naphthalene, is alkylated by an olefin, alkyl halide or alcohol in
the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and
Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See
Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many
homogeneous or heterogeneous, solid catalysts are known to one
skilled in the art. The choice of catalyst depends on the
reactivity of the starting materials and product quality
requirements. For example, strong acids such as AlCl3, BF3, or HF
may be used. In some cases, milder catalysts include FeCl3 or
SnCl4. Newer alkylation technology uses zeolites or solid super
acids.
[0021] Esters may also comprise a useful base stock, for example
esters such as the esters of dibasic acids with monoalkanols and
the polyol esters of monocarboxylic acids. Esters of the former
type include, for example, the esters of dicarboxylic acids such as
phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic
acid, maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acid, alkenyl malonic acid, etc., with a variety of
alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol,
2-ethylhexyl alcohol, etc. Specific examples of these types of
esters include dibutyl adipate, di-(2-ethylhexyl) sebacate,
di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,
diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, etc.
[0022] Particularly useful synthetic esters may be those which are
obtained by reacting one or more polyhydric alcohols, for example
hindered polyols (such as the neopentyl polyols, e.g., neopentyl
glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,
trimethylol propane, pentaerythritol and dipentaerythritol) with
alkanoic acids containing at least 4 carbon atoms, for instance C5
to C30 acids such as saturated straight chain fatty acids including
caprylic acid, capric acid, lauric acid, myristic acid, palmitic
acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid, or mixtures of any of these materials.
[0023] Suitable synthetic ester components include the esters of
trimethylol propane, trimethylol butane, trimethylol ethane,
pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from 5 to 10 carbon atoms. These
esters are widely available commercially, for example, the Mobil
P-41 and P-51 esters of ExxonMobil Chemical Company. In a certain
embodiment, a synthetic ester includes trimethylolpropane
trinonoate.
[0024] Also useful are esters derived from renewable material such
as coconut, palm, rapeseed, soy, sunflower and the like. These
esters may be monoesters, di-esters, polyol esters, complex esters,
or mixtures thereof. These esters are widely available
commercially, for example, the Mobil P-51 ester of ExxonMobil
Chemical Company.
[0025] In certain embodiments, diesters are suitable base stocks
and may be formed by esterification of linear or branched C6-C15
aliphatic alcohols with one or more dibasic acids such as adipic,
sebacic or azelaic acids. Examples of diesters are di-2-ethylhexyl
sebacate and dioctyl adipate. A synthetic polyol ester base oil may
be formed by esterification of an aliphatic polyol with carboxylic
acid. An aliphatic polyol may contain from 4 to 15 carbon atoms and
have from 2 to 8 hydroxyl groups. Examples of polyols include
trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl
glycol, tripentaerythritol and mixtures thereof.
[0026] In certain embodiments, a carboxylic acid reactant used to
produce a synthetic polyol ester base oil is selected from
aliphatic monocarboxylic acid or a mixture of aliphatic
monocarboxylic acid and aliphatic dicarboxylic acid. The carboxylic
acid may contain from 4 to 12 carbon atoms and may be straight or
branched chain aliphatic acids. Mixtures of monocarboxylic acids
may be used. In one embodiment, a polyol ester base oil is prepared
from technical pentaerythritol and a mixture of C4-C12 carboxylic
acids. Technical pentaerythritol is a mixture that includes about
85 to about 92 wt % monopentaerythritol and about 8 to about 15 wt
% dipentaerythritol. A typical commercial technical pentaerythritol
contains about 88 wt % monopentaerythritol and about 12 wt % of
dipentaerythritol.
[0027] Other useful fluids of lubricating viscosity include
non-conventional or unconventional base stocks that have been
processed, e.g. catalytically, or synthesized to provide high
performance lubrication characteristics.
[0028] Non-conventional base stocks/base oils include one or more
of a mixture of base stock(s) derived from one or more
Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate
base stock(s) derived from natural wax or waxy feeds, mineral and
or non-mineral oil waxy feed stocks such as slack waxes, natural
waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker
bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other
mineral, mineral oil, or even non-petroleum oil derived waxy
materials such as waxy materials received from coal liquefaction or
shale oil, and mixtures of such base stocks.
[0029] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and/or base oils
are GTL materials of lubricating viscosity that are generally
derived from hydrocarbons; for example, waxy synthesized
hydrocarbons, that are themselves derived from simpler gaseous
carbon-containing compounds, hydrogen-containing compounds and/or
elements as feed stocks. GTL base stock(s) and/or base oil(s)
include oils boiling in the lube oil boiling range (1)
separated/fractionated from synthesized GTL materials such as, for
example, by distillation and subsequently subjected to a final wax
processing step which involves either or both of a catalytic
dewaxing process, or a solvent dewaxing process, to produce lube
oils of reduced/low pour point; (2) synthesized wax isomerates,
comprising, for example, hydrodewaxed or hydroisomerized cat and/or
solvent dewaxed synthesized wax or waxy hydrocarbons; (3)
hydrodewaxed or hydroisomerized cat and/or solvent dewaxed
Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); for example
hydrodewaxed or hydroisomerized/followed by cat and/or solvent
dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T
waxes, or mixtures thereof.
[0030] GTL base stock(s) and/or base oil(s) derived from GTL
materials, especially, hydrodewaxed or hydroisomerized/followed by
cat and/or solvent dewaxed wax or waxy feed, for example F-T
material derived base stock(s) and/or base oil(s), are
characterized typically as having kinematic viscosities at
100.degree. C. of from about 2 mm.sup.2/s to about 50 mm.sup.2/s
(ASTM D445). They are further characterized typically as having
pour points of about -5.degree. C. to about -40.degree. C. or lower
(ASTM D97). They may also be characterized as having viscosity
indices of 80 to 140 or greater (ASTM D2270).
[0031] The term GTL base stock and/or base oil and/or wax isomerate
base stock and/or base oil is to be understood as embracing
individual fractions of such materials of wide viscosity range as
recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low
viscosity fractions with one, two or more higher viscosity
fractions to produce a blend wherein the blend exhibits a target
kinematic viscosity.
[0032] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived may advantageously be an F-T material
(i.e., hydrocarbons, waxy hydrocarbons, wax).
[0033] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) and hydrodewaxed, or
hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or
base oil(s) typically have very low sulfur and nitrogen content,
generally containing less than 10 ppm, and more typically less than
5 ppm of each of these elements. The sulfur and nitrogen content of
GTL base stock(s) and/or base oil(s) obtained from F-T material,
especially F-T wax, is essentially nil. In addition, the absence of
phosphorous and aromatics make this material especially suitable
for the formulation of low sulfur, sulfated ash, and phosphorus
(low SAP) products.
[0034] Base oils for use in the formulated lubricating oils useful
in the present disclosure are any of the variety of oils
corresponding to API Group I, Group I, Group III, Group IV, and
Group V oils and mixtures thereof, in some embodiments API Group
II, Group III, Group IV, and Group V oils and mixtures thereof, in
certain embodiments the Group III to Group V base oils due to their
exceptional volatility, stability, viscometric and cleanliness
features. Minor quantities of Group I stock, such as the amount
used to dilute additives for blending into formulated lube oil
products, can be tolerated but should be kept to a minimum, i.e.
amounts only associated with their use as diluent/carrier oil for
additives used on an "as-received" basis. In regard to the Group II
stocks, in some embodiments the Group II stock may be in the higher
quality range associated with that stock, i.e. a Group II stock
having a viscosity index in the range 100 cSt<VI<120 cSt.
[0035] The lubricating base oil or base stock constitutes the major
component of the lubricant composition of the present disclosure.
In an embodiment, a lubricating oil base stock for the inventive
lubricant composition is from any of about 80 wt % (weight
percent), about 81 wt %, about 82 wt %, about 83 wt %, about 84 wt
%, about 85 wt %, about 86 wt %, about 87 wt % or about 88 wt % to
any of about 89 wt %, about 90 wt %, about 91 wt %, about 92 wt %,
about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt %, about
97 wt %, about 98 wt %, about 99 wt %, about 99.1 wt %, about 99.2
wt %, about 99.3 wt %, about 99.4 wt %, about 99.5 wt %, about 99.6
wt % or about 99.7 wt %, based on the total weight of the fully
formulated lubricant composition.
[0036] Group III base stocks may be GTL and Yubase Plus
(hydroprocessed base stock). Group V base stocks may include
alkylated naphthalene, synthetic esters and combinations
thereof.
[0037] In some embodiments, the base oils or base stocks described
above have a kinematic viscosity, according to ASTM standards, of
about 2.5 cSt or about 4 cSt to any of about 6 cSt, about 8 cSt or
about 9 cSt, about 12 cSt (or mm.sup.2/s) at 100.degree. C. In
other embodiments, base stocks may have a kinematic viscosity of up
to about 100 cSt, about 150 cSt, about 200 cSt, about 250 cSt or
about 300 cSt at 100.degree. C.
[0038] In some embodiments, a base stock may comprise a random or
block polyalkylene glycol copolymer comprising ethylene oxide and
propylene oxide units. A copolymer may comprise from any of about
30 wt %, about 50 wt % or about 60 wt % to any of about 70 wt %,
about 85 wt % or about 95 wt % ethylene oxide units with the
remainder being propylene oxide units.
[0039] In certain embodiments, a base oil comprises those selected
from the group consisting of API groups II III and IV. Included are
GTL derived base oils. One or more base oils selected from groups
II, III and IV may be combined with one or more esters as described
above, for instance one or more diesters and/or triesters. In such
mixtures, an ester may be present from any of about 0.5 wt %, about
1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %,
about 6 wt %, about 7 wt % or about 8 wt % to any of about 9 wt %,
about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about
14 wt % or about 15 wt %, based on a fully formulated lubricating
oil.
[0040] In some embodiments, the lubricant composition may comprise
a diester component having the following structure:
##STR00001##
[0041] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently a straight or branched chain C.sub.2 to C.sub.17
hydrocarbon group.
[0042] In some embodiments, R.sub.1, R.sub.2, R.sub.3 and R.sub.4
are selected such that the kinematic viscosity of the composition
at a temperature of 100.degree. C. is about 3 mm.sup.2/sec or
greater. In some or other embodiments, R.sub.1, R.sub.2, R.sub.3
and R.sub.4 are selected such that the pour point of the resulting
formulated oil is about -10.degree. C. or lower, about -25.degree.
C. or lower or about -40.degree. C. or lower. In some embodiments,
R.sub.1 and R.sub.2 are selected to have a combined carbon number
(i.e., total number of carbon atoms) of from 6 to 14. In these or
other embodiments, R.sub.3 and R.sub.4 are selected to have a
combined carbon number of from 10 to 34. Depending on the
embodiment, such resulting diester species can have a molecular
mass from about 340 atomic mass units (amu) to about 780 amu.
[0043] In some embodiments, a diester component is substantially
homogeneous. In some or other embodiments, a diester component
comprises a variety (i.e., a mixture) of diester species.
[0044] In some embodiments, the diester component comprises at
least one diester species derived from a C.sub.8 to C.sub.16 olefin
and a C.sub.2 to C.sub.18 carboxylic acid. A diester species may be
prepared by reacting each --OH group (on the intermediate) with a
different acid, but such diester species can also be made by
reacting each --OH group with the same acid.
[0045] In some embodiments, a diester component in the lubricant
composition comprises a diester species selected from the group
consisting of decanoic acid 2-deanoyloxy-1-hexyl-octyl ester and
its isomers, tetradecanoic acid-1-hexyl-2-tetradecanoyloxy-octyl
esters and its isomers, dodecanoic acid
2-dodecanoylaxy-1-hexyl-octyl ester and its isomers, hexanoic acid
2-hexanoyloxy-1-hexy-octyl ester and its isomers, octanoic acid
2-octanoyloxy-1-hexyl-octyl ester and its isomers, hexanoic acid
2-hexanoyloxy-1-pentyl-heptyl ester and isomers, octanoic acid
2-octanoyloxy-1-pentyl-heptyl ester and isomers, decanoic acid
2-decanoyloxy-1-pentyl-heptyl ester and isomers, decanoic
acid-2-cecanoyloxy-1-pentyl-heptyl ester and its isomers,
dodecanoic acid-2-dodecanoyloxy-1-pentyl-heptyl ester and isomers,
tetradecanoic acid 1-pentyl-2-tetradecanoyloxy-heptyl ester and
isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxy-hexy ester
and isomers, dodecanoic acid-1-butyl-2-dodecanoyloxy-hexyl ester
and isomers, decanoic acid 1-butyl-2-decanoyloxy-hexyl ester and
isomers, octanoic acid 1-butyl-2-octanoyloxy-hexyl ester and
isomers, hexanoic acid 1-butyl-2-hexanoyloxy-hexyl ester and
isomers, tetradecanoic acid 1-propyl-2-tetradecanoyloxy-pentyl
ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl
ester and isomers, decanoic acid 2-decanoyloxy-1-propyl-pentyl
ester and isomers, octanoic acid 1-2-octanoyloxy-1-propyl-pentyl
ester and isomers, hexanoic acid 2-hexanoyloxy-1-propyl-pentyl
ester and isomers and mixtures thereof.
[0046] Methods which can be employed in making diesters suitable
for the lubricant composition described herein are further
described for example in U.S. Patent Application Publications
2009/0159837 and 2009/0198075. More specifically, in some
embodiments, processes for making diester species comprise:
epoxidizing an olefin (or quantity of olefins) having a carbon
number of from 8 to 16 to form an epoxide comprising an epoxide
ring; opening the epoxide ring to form a diol; and esterifying
(i.e., subjecting to esterification) the diol with an esterifying
species to form a diester species, wherein such esterifying species
are selected from the group consisting of carboxylic acids, acyl
acids, acyl halides, acyl anhydrides and combinations thereof,
wherein such esterifying species have a carbon number from 2 to 18;
and wherein the diester species have a viscosity of about 3
mm.sup.2/sec or more at a temperature of 100.degree. C.
[0047] Diester species may be prepared by epoxidizing an olefin
having from about 8 to about 16 carbon atoms to form an epoxide
comprising an epoxide ring. The epoxidized olefin is reacted
directly with an esterifying species to form a diester species,
wherein the esterifying species is selected from the group
consisting of carboxylic acids, acyl halides, acyl anhydrides, and
combinations thereof, wherein the esterifying species has a carbon
number of from 2 to 18, and wherein the diester species has a
viscosity and a pour point suitable for use as a finished oil.
[0048] In some embodiments, the olefin used is a reaction product
of a Fischer-Tropsch process. In these or other embodiments, the
carboxylic acid can be derived from alcohols generated by a
Fischer-Tropsch process and/or it can be a bio-derived fatty
acid.
[0049] In some embodiments, the olefin is an .alpha.-olefin (i.e.,
an olefin having a double bond at a chain terminus). In such
embodiments, it is usually necessary to isomerize the olefin so as
to internalize the double bond. Such isomerization is typically
carried out catalytically using a catalyst such as, but not limited
to, crystalline aluminosilicate and like materials and
aluminophosphates. See, e.g., U.S. Pat. Nos. 2,537,283; 3,211,801;
3,270,085; 3,327,014; 3,304,343; 3,448,164; 4,593,146; 3,723,564
and 6,281,404.
[0050] Fischer-Tropsch alpha olefins (.alpha.-olefins) can be
isomerized to the corresponding internal olefins followed by
epoxidation. The epoxides can then be transformed to the
corresponding diols via epoxide ring opening followed by
di-acylation (i.e., di-esterification) with the appropriate
carboxylic acids or their acylating derivatives. It is typically
necessary to convert alpha olefins to internal olefins because
diesters of alpha olefins, especially short chain alpha olefins,
tend to be solids or waxes. "Internalizing" alpha olefins followed
by transformation to the diester functionalities introduces
branching along the chain which reduces the pour point of the
intended products. The ester groups with their polar character
would further enhance the viscosity of the final product. Adding
ester branches will increase the carbon number and hence viscosity.
It can also decrease the associated pour and cloud points. In some
embodiments, there may be a few longer branches rather than many
short branches, as increased branching tends to lower the viscosity
index (VI).
[0051] Regarding the step of epoxidizing (i.e., the epoxidation
step), in some embodiments, the above-described olefin (in one
embodiment an internal olefin) can be reacted with a peroxide
(e.g., H.sub.2O.sub.2) or a peroxy acid (e.g., peroxyacetic acid)
to generate an epoxide. See, e.g., D. Swern, in Organic Peroxides
Vol. II, Wiley-Interscience, New York, 1971, pp. 355-533; and B.
Plesnicar, in Oxidation in Organic Chemistry, Part C, W.
Trahanovsky (ed.), Academic Press, New York 1978, pp. 221-253.
Olefins can be efficiently transformed to the corresponding diols
by highly selective reagent such as osmium tetra-oxide (M.
Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium
permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of
Organic Compounds, pp. 162-171 and 294-296, Academic Press, New
York, 1981).
[0052] Regarding the step of epoxide ring opening to the
corresponding diol, this step can be acid-catalyzed or
based-catalyzed hydrolysis. Exemplary acid catalysts include, but
are not limited to, mineral-based Bronsted acids (e.g., HCl,
H.sub.2SO.sub.4, H.sub.3PO.sub.4, perhalogenates, etc.), Lewis
acids (e.g., TiCl.sub.4 and AlCl.sub.3) solid acids such as acidic
aluminas and silicas or their mixtures, and the like. See, e.g.,
Chem. Rev. vol. 59, p. 737, 1959; and Angew. Chem. Int. Ed., vol.
31, p. 1179, 1992. Based-catalyzed hydrolysis typically involves
the use of bases such as aqueous solutions of sodium or potassium
hydroxide.
[0053] Regarding the step of esterifying (esterification), an acid
is typically used to catalyze the reaction between the --OH groups
of the diol and the carboxylic acid(s). Suitable acids include, but
are not limited to, sulfuric acid (Munch-Peterson, Org. Synth., V,
p. 762, 1973), sulfonic acid (Allen and Sprangler, Org. Synth.,
III, p. 203, 1955), hydrochloric acid (Eliel et al., Org. Synth.,
IV, p. 169, 1963), and phosphoric acid (among others). In some
embodiments, the carboxylic acid used in this step is first
converted to an acyl chloride (via, e.g., thionyl chloride or
PCl3). Alternatively, an acyl chloride could be employed directly.
Wherein an acyl chloride is used, an acid catalyst is not needed
and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or
triethylamine (TEA) is typically added to react with an HCl
produced. When pyridine or DMAP is used, it is believed that these
amines also act as a catalyst by forming a more reactive acylating
intermediate. See, e.g., Fersh et al., J. Am. Chem. Soc., vol. 92,
pp. 5432-5442, 1970; and Hofle et al., Angew. Chem. Int. Ed. Engl.,
vol. 17, p. 569, 1978.
[0054] Regardless of the source of the olefin, in some embodiments,
the carboxylic acid used in the above-described method is derived
from biomass. In some such embodiments, this involves the
extraction of some oil (e.g., triglyceride) component from the
biomass and hydrolysis of the triglycerides of which the oil
component is comprised so as to form free carboxylic acids.
[0055] In some embodiments, the lubricant composition may comprise
a triester component having the following chemical structure:
##STR00002##
[0056] Wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from C.sub.2 to C.sub.2 hydrocarbon groups
(hydrocarbon groups with from 2 to 20 carbon atoms), and wherein
"n" is an integer from 2 to 20.
[0057] Selection of R.sub.1, R.sub.2, R.sub.3 and R.sub.4, and n
can follow any or all of several criteria. For example, in some
embodiments, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 and n are
selected such that the kinematic viscosity of the composition at a
temperature of 100.degree. C. is typically about 3 mm.sup.2/sec or
greater. In some or other embodiments, R.sub.1, R.sub.2, R.sub.3,
and R.sub.4 and n are selected such that the pour point of the
resulting finished oil is about -10.degree. C. or lower, e.g.,
about -25.degree. C. or about -40.degree. C. or lower. In some
embodiments, R.sub.1 is selected to have a total carbon number of
from 6 to 12. In these or other embodiments, R.sub.2 is selected to
have a carbon number of from 1 to 20. In these or other
embodiments, R.sub.3 and R.sub.4 are selected to have a combined
carbon number of from 4 to 36. In these or other embodiments, n is
selected to be an integer from 5 to 10. Depending on the
embodiment, such resulting triester species can typically have a
molecular mass from about 400 amu or about 450 amu to about 1000
amu or about 1100 amu.
[0058] In some embodiments, the ester component may be
substantially homogeneous in terms of its triester component. In
some other embodiments, the triester component comprises a variety
(i.e., a mixture) of triester species. In these or other
embodiments, such above-described triester components further
comprise one or more triester species.
[0059] In some of the above-described embodiments, a triester
component comprises one or more triester species of the type
9,10-bis-alkanoyloxy-oetadecanoic acid alkyl ester and isomers and
mixtures thereof, where the alkyl is selected from the group
consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, and octadecyl; and where the alkanoyloxy is
selected from the group consisting of ethanoyloxy, propanoyoxy,
butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy,
nonaoyloxy, decanoyloxy, undacanoyloxy, dodecanoyloxy,
tridecanoyloxy, tetradecanoyloxy, pentaclecanoyloxy,
hexadeconoyloxy, and octadecanoyloxy,
9,10-bis-hexanoyloxy-octadecanoic acid hexyl ester and
9,10-bis-decanoyloxy-octadecanoic acid decyl ester are exemplary
such triesters.
[0060] One method of preparing triester species is described in
U.S. Pat. No. 7,544,645. In some embodiments, processes for making
triester species comprises the steps: esterifying (i.e., subjecting
to esterification) a mono-unsaturated fatty acid (or quantity of
mono-unsaturated fatty acids) having a carbon number of from 10 to
22 with an alcohol to form an unsaturated ester (or a quantity
thereof); epoxidizing the unsaturated ester to form an epoxy-ester
species comprising an epoxide ring; opening the epoxide ring of the
epoxy-ester species to form a dihydroxy-ester: and esterifying the
dihydroxy-ester with an esterifying species to form a triester
species, wherein such esterifying species are selected from the
group consisting of carboxylic acids, acyl halides, acyl
anhydrides, and combinations thereof, and wherein such esterifying
species have a carbon number of from 2 to 19.
[0061] In another embodiment, the method can comprise reducing a
monosaturated fatty acid to the corresponding unsaturated alcohol.
The unsaturated alcohol is then epoxidized to an epoxy fatty
alcohol. The ring of the epoxy fatty alcohol is opened to make the
corresponding triol; and then the triol is esterified with an
esterifying species to form a triester species, wherein the
esterifying species is selected from the group consisting of
carboxylic acids, acyl halides, acyl anhydrides and combinations
thereof, and wherein the esterifying species has a carbon number of
from 2 to 19. The structure of a triester prepared by the foregoing
method would be as follows:
##STR00003##
[0062] wherein R.sub.2, R.sub.3 and R.sub.4 are independently
selected from C.sub.2 to C.sub.2 hydrocarbon groups, for instance
selected from C.sub.4 to C.sub.12 hydrocarbon groups.
[0063] In another embodiment, the method can comprise reducing a
monosaturated fatty acid to the corresponding unsaturated alcohol;
epoxidizing the unsaturated alcohol to an epoxy fatty alcohol; and
esterifying the fatty alcohol epoxide with an esterifying species
to form a triester species, wherein the esterifying species is
selected from the group consisting of carboxylic acids, acyl
halides, acyl anhydrides, and combinations thereof and wherein the
esterifying species has a carbon number of from 2 to 19.
[0064] In some embodiments, where a quantity of triester species is
formed, the quantity of triester species can be substantially
homogeneous, or it can be a mixture of two or more different such
triester species. Additionally or alternatively, in some
embodiments, such methods further comprise a step of blending a
triester composition(s) with one or more diester species.
[0065] In some embodiments, such methods produce compositions
comprising at least one triester species of the type
9,10-bis-alkanoyloxy-octadecanoic acid alkyl ester and isomers and
mixtures thereof where the alkyl is selected from the group
consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl and octadecyl; and where the alkanoyloxy is
selected from the group consisting of ethanoyloxy, propanoyoxy,
butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy,
nonaoyloxy, decanoyloxy, undacanoyloxy, dodecanoyloxy,
tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy,
hexadeconoyloxy, and octadecanoyloxy. Exemplary such triesters
include, but not limited to, 9,10-bis-hexanoyloxy-octadecanoic acid
hexyl ester; 9,10-bis-octanoyloxy-octadecanoic acid hexyl ester;
9,10-bis-decanoyloxy-octadecanoic acid hexyl ester;
9,10-bis-dodecanoyoxy-octadecanoic acid hexyl ester;
9,10-bis-hexanoyloxy-octadecanoic acid decyl ester;
9,10-bis-decanoyloxy-octadecanoic acid decyl ester;
9,10-bis-octanoyloxy-octadecanoic acid decyl ester;
9,10-bis-dodecanoyloxy-octadecanoic acid decyl ester;
9,10-bis-hexanoyloxy-octadecanoic acid octyl ester;
9,10-bis-octanoyloxy-octadecanoic acid octyl ester:
9,10-bis-decanoyloxy-octadecanoic acid octyl ester;
9,10-bis-dodecanoyloxy-octadecanoic acid octyl ester;
9,10-bis-hexanoyloxy-octadecanoic acid dodecyl ester;
9,10-bis-octanoyloxy-octadecanoic acid dodecyl ester;
9,10-bis-decanoyloxy-octadecanoic acid dodecyl ester;
9,10-bis-doclecanoyloxy-octadecanoic acid dodecyl ester; and
mixtures thereof.
[0066] In some such above-described method embodiments, the
mono-unsaturated fatty acid can be a bio-derived fatty acid. In
some or other such above-described method embodiments, the
alcohol(s) can be FT-produced alcohols.
[0067] In some method embodiments, the step of esterifying (i.e.,
esterification) the mono-unsaturated fatty acid can proceed via an
acid-catalyzed reaction with an alcohol using, e.g., H2SO4 as a
catalyst. In some or other embodiments, the esterifying can proceed
through a conversion of the fatty acid(s) to an acyl halide
(chloride, bromide, or iodide) or acyl anhydride, followed by
reaction with an alcohol.
[0068] Regarding the step of epoxidizing (i.e., the epoxidation
step), in some embodiments, the above-described mono-unsaturated
ester can be reacted with a peroxide (e.g., H.sub.2O.sub.2) or a
peroxy acid (e.g., peroxyacetic acid) to generate an epoxy-ester
species. See, e.g., D. Swern, in Organic Peroxides Vol. II,
Wiley-Interscience, New York, 1971, pp. 355-533; and B. Plesnicar,
in Oxidation in Organic Chemistry, Part C, W. Trahanovsky (ed.),
Academic Press, New York 1978, pp. 221-253. Additionally or
alternatively, the olefinic portion of the mono-unsaturated ester
can be efficiently transformed to the corresponding dihydroxy ester
by highly selective reagents such as osmium tetra-oxide (M.
Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium
permanganate (Sheldon and Kochi, in Metal-Catalyzed Oxidation of
Organic Compounds, pp. 162-171 and 294-296, Academic Press, New
York, 1981).
[0069] Regarding the step of epoxide ring opening to the
corresponding dihydroxy-ester, this step is usually an
acid-catalyzed hydrolysis. Exemplary acid catalysts include, but
are not limited to, mineral-based Bronsted acids (e.g., HCl, H2SO4,
H3PO4, perhalogenates, etc.), Lewis acids (e.g., TiCl4 and AlCl3),
solid acids such as acidic aluminas and silicas or their mixtures,
and the like. See, e.g., Chem. Rev. vol. 59, p. 737, 1959; and
Angew. Chem. Int. Ed., vol. 31, p. 1179, 1992. The epoxide ring
opening to the diol can also be accomplished by base-catalyzed
hydrolysis using aqueous solutions of KOH or NaOH.
[0070] Regarding the step of esterifying the dihydroxy-ester to
form a triester, an acid is typically used to catalyze the reaction
between the --OH groups of the diol and the carboxylic acid(s).
Suitable acids include, but are not limited to, sulfuric acid
(Munch-Peterson, Org. Synth., V, p. 762, 1973), sulfonic acid
(Allen and Sprangler, Org Synth., III, p. 203, 1955), hydrochloric
acid (Eliel et al., Org Synth., IV, p. 169, 1963), and phosphoric
acid (among others). In some embodiments, the carboxylic acid used
in this step is first converted to an acyl chloride (or another
acyl halide) via, e.g., thionyl chloride or PCl3. Alternatively, an
acyl chloride (or other acyl halide) could be employed directly.
Where an acyl chloride is used, an acid catalyst is not needed and
a base such as pyridine, 4-dimethylaminopyridine (DMAP) or
triethylamine (TEA) is typically added to react with an HCl
produced. When pyridine or DMAP is used, it is believed that these
amines also act as a catalyst by forming a more reactive acylating
intermediate. See, e.g., Fersh et al., J. Am. Chem. Soc., vol. 92,
pp. 5432-5442, 1970; and Hofle et al., Angew. Chem. Int. Ed. Engl.,
vol. 17, p. 569, 1978. Additionally or alternatively, the
carboxylic acid could be converted into an acyl anhydride and/or
such species could be employed directly.
[0071] Regardless of the source of the mono-unsaturated fatty acid,
in some embodiments, the carboxylic acids (or their acyl
derivatives) used in the above-described methods may be derived
from biomass. In some such embodiments, this involves the
extraction of some oil (e.g., triglyceride) component from the
biomass and hydrolysis of the triglycerides of which the oil
component is comprised so as to form free carboxylic acids.
[0072] In some particular embodiments, wherein the above-described
method uses oleic acid for the mono-unsaturated fatty acid, the
resulting triester is of the type:
##STR00004##
[0073] wherein R.sub.2, R.sub.3 and R.sub.4 are independently
selected from C.sub.2 to C.sub.20 hydrocarbon groups, for instance
selected from C.sub.4 to C.sub.12 hydrocarbon groups.
[0074] Using a synthetic strategy in accordance with that outlined
above, oleic acid can be converted to triester derivatives
(9,10-bis-hexanoyloxy-octadecanoic acid hexyl ester) and
(9,10-bis-decanoyloxy-octadecanoic acid decyl ester). Oleic acid is
first esterified to yield a mono-unsaturated ester. The
mono-unsaturated ester is subjected to an epoxidation agent to give
an epoxy-ester species, which undergoes ring-opening to yield a
dihydroxy ester, which can then be reacted with an acyl chloride to
yield a triester product.
[0075] The strategy of the above-described synthesis utilizes the
double bond functionality in oleic acid by converting it to the
diol via double bond epoxidation followed by epoxide ring opening.
Accordingly, the synthesis begins by converting oleic acid to the
appropriate alkyl oleate followed by epoxidation and epoxide ring
opening to the corresponding diol derivative (dihydroxy ester).
[0076] Variations (i.e., alternate embodiments) on the
above-described processes include, but are not limited to,
utilizing mixtures of isomeric olefins and or mixtures of olefins
having a different number of carbons. This may lead to diester
mixtures and triester mixtures in an ester component.
[0077] Variations on the above-described processes include, but are
not limited to, using carboxylic acids derived from FT alcohols by
oxidation.
[0078] In some embodiments, a base stock comprises a mixture of one
or more PAOs and one or more esters.
[0079] In some embodiments, an ashless lubricant composition for
use in an internal combustion engine may comprise one or more
antioxidants selected from the group consisting of alkylated
phenyl-naphthyl amine antioxidants, diphenylamine antioxidants,
polymerized diphenylamine antioxidants, phenolic antioxidants, and
combinations thereof.
[0080] A suitable exemplary alkylated phenyl-naphthyl amine
antioxidant may comprise N-.alpha.-naphthyl-N-phenylamine
antioxidants (PANA) of formula
##STR00005##
[0081] Wherein R is H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl, C.sub.2-C.sub.18 alkynyl, --C(O)C.sub.1-C.sub.18 alkyl or
--C(O)aryl and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each
independently H, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl.
[0082] In some embodiments, PANA antioxidants are of formula
##STR00006##
[0083] Wherein R.sub.1 and R.sub.2 are each independently H or
C.sub.1-C.sub.18 alkyl. In certain embodiments R.sub.2 is H and
R.sub.1 is a branched chain C.sub.4-C.sub.12 alkyl, for example
t-butyl, t-octyl or branched nonyl.
[0084] Diphenylamine (DPA) antioxidants may be of formula
##STR00007##
[0085] Wherein R is H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl, C.sub.2-C.sub.1 alkynyl, --C(O)C.sub.1-C.sub.18 alkyl or
--C(O)aryl and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each
independently H, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl. These may
also be polymerized to form oligomers and polymers.
[0086] In certain embodiments, diphenylamine antioxidants may be of
formula
##STR00008##
[0087] wherein R.sub.1 and R.sub.2 are each independently H,
C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl or
C.sub.7-C.sub.21 aralkyl. In certain embodiments, R.sub.1 and
R.sub.2 are each independently H, tert-butyl, tert-octyl or
branched nonyl.
[0088] Alkyl groups are straight or branched chain and include
methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,
tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,
1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,
1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,
tert-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,
1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,
dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl and octadecyl. Alkyl groups
mentioned herein are linear or branched.
[0089] The alkyl portion of alkoxy, alkylamine, dialkylamino and
alkylthio groups are linear or branched and include the alkyl
groups mentioned above.
[0090] Alkenyl is an unsaturated alkyl, for instance allyl. Alkynyl
includes a triple bond.
[0091] Aralkyl includes benzyl, .alpha.-methylbenzyl,
.alpha.,.alpha.-dimethylbenzyl, 2-phenylethyl and
2-phenyl-2-propyl.
[0092] Cycloalkyl includes cyclopentyl, cyclohexyl and
cycloheptyl.
[0093] In some embodiments, an ashless lubricant composition for
use in internal combustion engine, as described herein, may
comprise one or more sulfur-containing additives that may act as
secondary antioxidants. Suitable sulfur-containing additives,
according to embodiments, may be sulfur containing additives that
comprise up to 7 carbon atoms. In one embodiment, the
sulfur-containing additive may be a sulfurized isobutylene (e.g.,
CAS #68425-15-0, CAS #68937-96-2, CAS #68511-50-2). The
sulfur-containing additive may be comprise a mixture of sulfur
compounds, e.g., with a varying number of sulfur atoms.
[0094] For instance, the mixture of sulfur compounds may comprise
sulfurized isobutylene with one sulfur atom, sulfurized isobutylene
with two sulfur atoms, sulfurized isobutylene with three sulfur
atoms, sulfurized isobutylene with four sulfur atoms, sulfurized
isobutylene with five sulfur atoms, and mixtures thereof.
[0095] In some embodiments, the mixture of sulfur compounds may
comprise: 1) from about 2.5% to about 12.5%, from about 5% to about
10%, or from about 7% to about 8% sulfurized isobutylene with one
sulfur atom; 2) from about 32.5% to about 42.5%, from about 35% to
about 40%, or from about 37% to about 38% sulfurized isobutylene
with two sulfur atoms; 3) from about 30% to about 40%, from about
32.5% to about 37.5%, or from about 34% to about 36% sulfurized
isobutylene with three sulfur atoms; 4) from about 5% to about 15%,
from about 7.5% to about 12.5%, or from about 9% to about 11%
sulfurized isobutylene with four sulfur atoms; 5) from about 1% to
about 11%, from about 4% to about 9%, or from about 6% to about 7%
of sulfurized isobutylene with five carbon atoms; or any mixture
thereof of any one of 1) through 5).
[0096] In some embodiments, the lubricant composition may further
comprise at least one additional sulfur-containing lubricant
additives including sulfur-containing hindered phenolic compounds
(e.g., CAS #41484-35-9), sulfur-containing rust inhibitors,
sulfur-containing friction modifiers and sulfur-containing antiwear
additives.
[0097] Sulfur-containing hindered phenolic compounds include
alkylthiomethylphenols, for example
2,4-di-octylthiomethyl-6-tert-butylphenol,
2,4-di-octylthiomethyl-6-methylphenol,
2,4-di-octylthiomethyl-6-ethylphenol or
2,6-di-dodecylthiomethyl-4-nonylphenol; hydroxylated thiodiphenyl
ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis-(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol) or
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; S-benzyl
compounds, for example octadecyl
4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl
4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide or isooctyl
3,5-di-tert-butyl-4-hydroxy-benzylmercaptoacetate; and esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid,
3,5-di-tert-butyl-4-hydroxyphenylacetic acid or
.beta.-(5-tert-butyl-4-hydroxyphenyl)-3-thiabutyric acid with
sulfur-containing mono- or polyhydric alcohols such as
thiodiethylene glycol, 3-thiaundecanol or thiapentadecanol.
[0098] Sulfur-containing rust inhibitors include, for example,
barium dinonylnaphthalene-sulfonates, calcium petroleumsulfonates,
alkylthio-substituted aliphatic carboxylic acids, esters of
aliphatic 2-sulfocarboxylic acids and salts thereof.
[0099] Sulfur-containing friction modifiers may for example be
selected from organomolybdenum dithiocarbamates, organomolybdenum
dithiophosphates and organomolybdenum compounds based on
dispersants and molybdenum disulfide.
[0100] Sulfur-containing antiwear additives include sulfurized
olefins and vegetable oils, dialkyldithiophosphate esters, zinc
dialkyldithiophosphates, alkyl and aryl di- and trisulfides,
derivatives of 2,5-dimercapto-1,3,4-thiadiazole,
ethyl(bisisopropyloxyphosphinothioyl)-thiopropionate, triphenyl
thiophosphate (triphenyl phosphorothioate), tris(alkylphenyl)
phosphorothioates and mixtures thereof (for example
tris(isononylphenyl) phosphorothioate), diphenylmonononylphenyl
phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the
dodecylamine salt of 3-hydroxy-1,3-thiaphosphetan 3-oxide,
trithiophosphoric acid 5,5,5-tris-isooctyl 2-acetate, derivatives
of 2-mercaptobenzothiazole, such as
1-N,N-bis(2-ethylhexyl)aminomethyl-2-mercapto-1H-1,3-benzothiazol-
e, and ethoxycarbonyl 5-octyldithiocarbamate; and dihydrocarbyl
dithiophosphate metal salts where the metal may be aluminum, lead,
tin manganese, cobalt, nickel, zinc or copper.
[0101] A zinc dialkyldithiophosphate salt may be represented as
##STR00009##
[0102] where R and R' are independently C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.20 alkenyl, C.sub.5-C.sub.12 cycloalkyl,
C.sub.7-C.sub.13 aralkyl or C.sub.6-C.sub.10 aryl, for example R
and R' are independently C.sub.1-C.sub.12 alkyl.
[0103] In some embodiments, the lubricants may be substantially
free or free of zinc dialkyldithiophosphates. The term
"substantially free" may mean "not intentionally added", for
example may mean .ltoreq.1000 ppm (0.1 wt %), .ltoreq.750 ppm
(0.075 wt %), .ltoreq.500 ppm (0.05 wt %), .ltoreq.250 ppm (0.025
wt %), .ltoreq.100 ppm (0.01 wt %), .ltoreq.75 ppm (0.0075 wt %),
.ltoreq.50 ppm (0.005 wt %), .ltoreq.25 ppm (0.0025 wt %),
.ltoreq.10 ppm (0.001 wt %), .ltoreq.5 ppm (0.0005 wt %), .ltoreq.2
ppm (0.0002 wt %) or .ltoreq.1 ppm (0.0001 wt %) of a zinc
dialkyldithiophosphate (or other referenced component) may be
present, by weight, based on the weight of the total
composition.
[0104] In some embodiments, the zinc dialkyldithiophosphate salts
in the lubricant composition described herein may deliver less than
about 500 ppm phosphorus, less than about 450 ppm phosphorus, less
than about 400 ppm phosphorus, less than about 350 ppm phosphorus,
less than about 300 ppm phosphorus, less than about 250 ppm
phosphorus, less than about 200 ppm phosphorus, less than about 150
ppm phosphorus, less than about 100 ppm phosphorus, or less than
about 50 ppm phosphorus, based on the total weight of the lubricant
composition.
[0105] A suitable dialkyldithiophosphate ester for the lubricant
compositions described herein may be represented as
##STR00010##
[0106] in which R.sub.5 and R.sub.6 independently of one another
are C.sub.3-C.sub.18 alkyl, C.sub.5-C.sub.12 cycloalkyl,
C.sub.5-C.sub.6 cycloalkylmethyl, C.sub.9-C.sub.10
bicycloalkylmethyl, C.sub.9-C.sub.10 tricycloalkylmethyl, phenyl or
C.sub.7-C.sub.24 alkylphenyl or together are
(CH.sub.3).sub.2C(CH.sub.2).sub.2 and R.sub.7 and R.sub.8 are
independently hydrogen or C.sub.1-C.sub.18 alkyl. For example, a
dialkyl dithiophosphate ester, CAS #268567-32-4.
[0107] In some embodiments, sulfur-containing additives include
sulfurized olefins. Suitable olefins include isobutylene, other
butylenes, pentenes, propene, mixtures thereof and oligomers
thereof. In a certain embodiment, the sulfur-containing additives
include sulfurized isobutylene. Sulfurized olefins are described
in, for example, U.S. Pat. Nos. 3,471,404, 3,697,499, 3,703,504,
4,194,980, 4,344,854, 5,135,670, 5,338,468 and 5,849,677.
Sulfurized olefins include sulfur-containing polyolefins, for
example sulfur-containing polyisobutylene compounds, for example,
as described in U.S. Pat. No. 6,410,491 and US2005/0153850. In
general, sulfurized olefins may be prepared by treating an olefin
or an olefinic oligomer or polymer, such as isobutylene or
polyisobutylene, with a source of sulfur such as elemental sulfur,
hydrogen sulfide or sulfuric acid. Sulfurized olefins include
sulfurized polyolefins, for example sulfurized isobutylene includes
sulfurized polyisobutylene.
[0108] In certain embodiments, sulfur-containing additives may
include one or more di-tert-alkyl polysulfides such as
di-tert-butyl polysulfide (CAS #68937-96-2), di-tert-dodecyl
polysulfide (CAS #68425-15-0) or di-tert-nonyl polysulfide.
[0109] The one or more antioxidants, together in total, may be
present from any of about 0.20 wt % (weight percent), about 0.25 wt
%, about 0.30 wt %, about 0.35 wt %, about 0.40 wt %, about 0.45 wt
%, about 0.50 wt %, about 0.55 wt %, about 0.60 wt %, about 0.65 wt
%, about 0.70 wt %, about 0.75 wt %, about 0.80 wt %, about 0.85 wt
%, about 0.90 wt %, about 0.95 wt %, about 1.0 wt %, about 1.25 wt
%, about 1.50 wt %, about 1.75 wt %, about 2.0 wt %, about 2.25 wt
%, about 2.50 wt %, about 2.75 wt %, about 3.0 wt %, about 3.25 wt
%, about 3.50 wt %, about 3.75 wt %, about 4.0 wt %, about 4.25 wt
%, about 4.50 wt %, about 4.75 wt %, or about 6.0 wt %, up to any
of about 6.25 wt %, about 6.50 wt %, about 6.75 wt %, about 7.0 wt
%, about 7.25 wt %, about 7.50 wt %, about 7.75 wt %, about 8.0 wt
%, about 8.25 wt %, about 8.50 wt %, about 8.75 wt %, about 9.0 wt
%, about 9.25 wt %, about 9.50 wt %, about 9.75 wt %, or about 10.0
wt %, based on the total weight of the formulated lubricant
composition.
[0110] The one or more N-.alpha.-naphthyl-N-phenylamine
antioxidants and the one or more diphenylamine antioxidants may be
present in a weight/weight ratio of from any of about 1/9, about
1/8, about 1/7, about 1/6, about 1/5, about 1/4, about 1/3, about
1/2 or about 1/1 to any of about 2/1, about 3/1, about 4/1, about
5/1, about 6/1, about 7/1, about 8/1 or about 9/1. In certain
embodiments, the weight/weight ratio of the one or more
N-.alpha.-naphthyl-N-phenylamine antioxidants to the one or more
diphenylamine antioxidants may be from any of about 1/1, about 1/2,
about 1/3 or about 1/4 to any of about 1/5, about 1/6, about 1/7,
about 1/8 or about 1/9. In other embodiments, the weight/weight
ratio of the one or more N-.alpha.-naphthyl-N-phenylamine
antioxidants to the one or more diphenylamine antioxidants may be
from about 1/1 or about 1/2 to about 1/3.
[0111] The sulfur provided by the one or more sulfur-containing
additives may be present, in total, from any of about 50 ppm (parts
per million), about 75 ppm, about 100 ppm, about 125 ppm, about 150
ppm, about 175 ppm about 200 ppm, about 225 ppm, about 250 ppm,
about 275 ppm, about 300 ppm, about 325 ppm, about 350 ppm, about
375 ppm, about 400 ppm or about 425 ppm to any of about 450 ppm,
about 475 ppm, about 500 ppm, about 525 ppm, about 550 ppm, about
575 ppm, about 600 ppm, about 625 ppm, about 650 ppm, about 675
ppm, about 700 ppm, about 725 ppm, about 750 ppm, about 775 ppm,
about 800 ppm, about 825 ppm, about 850 ppm, about 875 ppm, about
900 ppm, about 925 ppm, about 950 ppm, about 975 ppm or, about 1000
ppm, by weight, based on the total weight of the lubricant
composition.
[0112] The lubricant compositions may further comprise one or more
non-sulfur-containing lubricant additives selected from the group
consisting of further antioxidants, antiwear agents (e.g., ashless
antiwear agents), dispersants, pour point depressants, detergents,
corrosion inhibitors, rust inhibitors, metal deactivators, extreme
pressure additives, anti-seizure agents, wax modifiers, viscosity
index improvers, viscosity modifiers, fluid-loss additives, seal
compatibility agents, friction modifiers, lubricity agents,
anti-staining agents, chromophoric agents, anti-foam agents,
demulsifiers, emulsifiers, densifiers, wetting agents, gelling
agents, tackiness agents, colorants and others.
[0113] In certain embodiments, lubricant compositions for use in an
internal combustion engine as described herein may comprise one or
more of an ashless antiwear component, dispersants, pour point
depressants, friction modifiers, and metal deactivators.
[0114] A suitable ashless antiwear component for an internal
combustion engine lubricant composition may comprise a phosphorus
derivative. The ashless antiwear component may be present in the
internal combustion engine lubricant composition in an amount
ranging from about 0.5 wt %, about 0.75 wt %, about 1.0 wt %, about
1.25 wt %, about 1.50 wt %, about 1.75 wt %, about 2.0 wt %, about
2.25 wt %, about 2.50 wt %, about 2.75 wt %, about 3.0 wt %, about
3.25 wt %, about 3.50 wt %, about 3.75 wt %, about 4.0 wt %, about
4.25 wt %, about 4.50 wt %, about 4.75 wt %, about 5.0 wt %, about
5.25 wt %, about 5.5 wt %, about 5.75 wt %, or about 6.0 wt %, up
to any of about 6.25 wt %, about 6.50 wt %, about 6.75 wt %, about
7.0 wt %, about 7.25 wt %, about 7.50 wt %, about 7.75 wt %, about
8.0 wt %, about 8.25 wt %, about 8.50 wt %, about 8.75 wt %, about
9.0 wt %, about 9.25 wt %, about 9.50 wt %, about 9.75 wt %, or
about 10.0 wt %, based on the total weight of the formulated
lubricant composition.
[0115] A suitable dispersant for an internal combustion engine
lubricant composition may be present in the lubricant composition
in an amount ranging from about 0.5 wt %, about 0.75 wt %, about
1.0 wt %, about 1.25 wt %, about 1.50 wt %, about 1.75 wt %, about
2.0 wt %, about 2.25 wt %, about 2.50 wt % up to any of about 2.75
wt %, about 3.0 wt %, about 3.25 wt %, about 3.50 wt %, about 3.75
wt %, about 4.0 wt %, about 4.25 wt %, about 4.50 wt %, about 4.75
wt %, or about 5.0 wt %.
[0116] A suitable pour point depressant for an internal combustion
engine lubricant composition may be present in the lubricant
composition in an amount ranging from about 0.05 wt %, about 0.075
wt %, about 0.10 wt % up to any of about 0.125 wt %, about 0.150 wt
%, about 0.175 wt %, or about 0.20 wt %.
[0117] A suitable friction modifier for an internal combustion
engine lubricant composition may be present in the lubricant
composition in an amount ranging from about 0.2 wt %, about 0.3 wt
%, about 0.4 wt %, about 0.5 wt % up to any of about 0.6 wt %,
about 0.7 wt %, about 0.8 wt %, or about 0.9 wt %.
[0118] A suitable metal deactivator for an internal combustion
engine lubricant composition may be present in the lubricant
composition in an amount ranging from about 0.1 wt %, about 0.2 wt
%, about 0.3 wt %, about 0.4 wt %, about 0.5 wt % up to any of
about 0.6 wt %, about 0.7 wt %, about 0.8 wt %, or about 0.9 wt
%.
[0119] In certain embodiments, disclosed is a process comprising
running an internal combustion engine with an ashless lubricant
composition. The ashless lubricant composition may be any one of
the lubricant compositions described herein. For instance, in
certain embodiments, the lubricant composition may comprise any of
the base oils described herein, one or more antioxidants selected
from the group consisting of alkylated phenyl-naphthyl amines
antioxidants antioxidants, diphenylamine antioxidants, phenolic
antioxidants, and combinations thereof, and one or more
sulfur-containing additives.
[0120] In certain embodiments, disclosed is a system comprising an
internal combustion engine and an ashless lubricant composition.
The ashless lubricant composition may be any one of the lubricant
compositions described herein. For instance, in certain
embodiments, the lubricant composition may comprise any of the base
oils described herein, one or more antioxidants selected from the
group consisting of alkylated phenyl-naphthyl amines antioxidants
antioxidants, diphenylamine antioxidants, phenolic antioxidants,
and combinations thereof, and one or more sulfur-containing
additives.
[0121] The term "base oil" is synonymous with "base stock",
"lubricating base oil" or "lubricating base stock".
[0122] The term "fully formulated lubricating oil" means a finished
lubricating oil for use containing a base stock and an additive
package and is synonymous with "formulated oil" or "finished
oil".
[0123] "Centistoke," abbreviated "cSt," is a unit for kinematic
viscosity of a fluid (e.g., a lubricant), wherein 1 centistoke
equals 1 millimeter squared per second (1 cSt=1 mm.sup.2/s).
[0124] The lubricant compositions in some embodiments have a
kinematic viscosity at 100.degree. C. of from any one of about 2
cSt, about 3 cSt, about 4 cSt, about 5 cSt, about 6 cSt or about 7
cSt to any one of about 8 cSt, about 9 cSt, about 10 cSt, about 11
cSt, about 12 cSt, about 13 cSt, about 14 cSt, about 15 cSt, about
16 cSt, about 17 cSt, about 18 cSt, about 19 cSt or about 20
cSt.
[0125] U.S. patents, U.S. patent applications and published U.S.
patent applications discussed herein are hereby incorporated by
reference.
[0126] Unless otherwise indicated, all parts and percentages are by
weight. Weight percent (wt %), if not otherwise indicated, is based
on an entire composition free of any volatiles.
[0127] For simplicity of explanation, the embodiments of the
methods of this disclosure are depicted and described as a series
of acts. However, acts in accordance with this disclosure can occur
in various orders and/or concurrently, and with other acts not
presented and described herein. Furthermore, not all illustrated
acts may be required to implement the methods in accordance with
the disclosed subject matter. In addition, those skilled in the art
will understand and appreciate that the methods could alternatively
be represented as a series of interrelated states via a state
diagram or events.
[0128] In the foregoing description, numerous specific details are
set forth, such as specific materials, dimensions, processes
parameters, etc., to provide a thorough understanding of the
present invention. The particular features, structures, materials,
or characteristics may be combined in any suitable manner in one or
more embodiments. The words "example" or "exemplary" are used
herein to mean serving as an example, instance, or illustration.
Any aspect or design described herein as "example" or "exemplary"
is not necessarily to be construed as preferred or advantageous
over other aspects or designs. Rather, use of the words "example"
or "exemplary" is intended to present concepts in a concrete
fashion. As used in this application, the term "or" is intended to
mean an inclusive "or" rather than an exclusive "or". That is,
unless specified otherwise, or clear from context, "X includes A or
B" is intended to mean any of the natural inclusive permutations.
That is, if X includes A; X includes B; or X includes both A and B,
then "X includes A or B" is satisfied under any of the foregoing
instances. Reference throughout this specification to "an
embodiment", "certain embodiments", or "one embodiment" means that
a particular feature, structure, or characteristic described in
connection with the embodiment is included in at least one
embodiment. Thus, the appearances of the phrase "an embodiment",
"certain embodiments", or "one embodiment" in various places
throughout this specification are not necessarily all referring to
the same embodiment.
[0129] The present invention has been described with reference to
specific exemplary embodiments thereof. The specification and
drawings are, accordingly, to be regarded in an illustrative rather
than a restrictive sense. Various modifications of the invention in
addition to those shown and described herein will become apparent
to those skilled in the art and are intended to fall within the
scope of the appended claims.
* * * * *
References