U.S. patent application number 16/720119 was filed with the patent office on 2020-06-25 for lubricating oil compositions with antioxidant formation and dissipation control.
The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to Andrew E. Taggi, Chengrong Wang.
Application Number | 20200199480 16/720119 |
Document ID | / |
Family ID | 69182696 |
Filed Date | 2020-06-25 |
![](/patent/app/20200199480/US20200199480A1-20200625-C00001.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00002.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00003.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00004.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00005.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00006.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00007.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00008.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00009.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00010.png)
![](/patent/app/20200199480/US20200199480A1-20200625-C00011.png)
View All Diagrams
United States Patent
Application |
20200199480 |
Kind Code |
A1 |
Taggi; Andrew E. ; et
al. |
June 25, 2020 |
LUBRICATING OIL COMPOSITIONS WITH ANTIOXIDANT FORMATION AND
DISSIPATION CONTROL
Abstract
A method for controlling formation and dissipation of at least
one oligomeric or polymeric aminic antioxidant in a lubricating
oil, during operation of an engine or other mechanical component
lubricated with the lubricating oil by using as the lubricating oil
a formulated oil. The formulated oil has a composition including a
lubricating oil base stock as a major component, and at least one
oligomeric or polymeric aminic antioxidant, as a minor component.
The at least one oligomeric or polymeric aminic antioxidant is
formed over time in situ from at least one monomeric aminic
antioxidant during operation of the engine or other mechanical
component. The at least one oligomeric or polymeric aminic
antioxidant is dissipated over time in the lubricating oil during
operation of the engine or other mechanical component. The at least
one monomeric aminic antioxidant is present in an amount from
greater than 2 to 10 wt. % of the lubricating oil.
Inventors: |
Taggi; Andrew E.; (New Hope,
PA) ; Wang; Chengrong; (Easton, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company |
Annandale |
NJ |
US |
|
|
Family ID: |
69182696 |
Appl. No.: |
16/720119 |
Filed: |
December 19, 2019 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62781720 |
Dec 19, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2215/066 20130101;
C10M 2217/046 20130101; C10N 2030/04 20130101; C10N 2030/10
20130101; C10M 149/22 20130101; C10M 169/044 20130101; C10M
2215/064 20130101; C10M 161/00 20130101; C10M 2215/26 20130101;
C10N 2040/25 20130101; C10M 133/12 20130101; C10M 2215/065
20130101; C10M 2203/003 20130101 |
International
Class: |
C10M 161/00 20060101
C10M161/00; C10M 169/04 20060101 C10M169/04; C10M 133/12 20060101
C10M133/12; C10M 149/22 20060101 C10M149/22 |
Claims
1. A method for controlling formation and dissipation of at least
one oligomeric or polymeric aminic antioxidant in a lubricating
oil, during operation of an engine or other mechanical component
lubricated with the lubricating oil by using as the lubricating oil
a formulated oil, said formulated oil having a composition
comprising a lubricating oil base stock as a major component; and
at least one oligomeric or polymeric aminic antioxidant, as a minor
component; wherein the at least one oligomeric or polymeric aminic
antioxidant is formed over time in situ from at least one monomeric
aminic antioxidant during operation of the engine or other
mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component; wherein the lubricating oil base stock is present in an
amount from about 1 to about 95 weight percent, based on the total
weight of the lubricating oil; and wherein the at least one
monomeric aminic antioxidant is present in an amount from greater
than about 2 to about 10 weight percent, based on the total weight
of the lubricating oil.
2. The method of claim 1 wherein, in measurements of the
lubricating oil by a Sequence IIIH engine test in accordance with
ASTM D8111-17, viscosity control and deposit control are improved
using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
3. The method of claim 1 wherein the at least one monomeric aminic
antioxidant comprises at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures
thereof.
4. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
5. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant comprises: ##STR00081## wherein (A)
and (B) each range from zero to 10, provided (A)+(B) is at least 2;
R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a styrene or C1
to C30 alkyl, q and y individually range from 0 to up to the
valence of the aryl group to which the respective R groups are
attached.
6. The method of claim 1 wherein the at least one monomeric aminic
antioxidant comprises: ##STR00082## wherein R is H, C.sub.4H.sub.9,
C.sub.8H.sub.17, or C.sub.9H.sub.19; and/or ##STR00083##
7. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of ##STR00084## wherein (A) and (B)
each range from zero to 10, provided (A)+(B) is at least 2; R.sup.2
is a styrene or C1 to C30 alkyl, R.sup.3 is a styrene or C1 to C30
alkyl, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
8. The method of claim 7 wherein the at least one oligomeric or
polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or
mixtures thereof.
9. The method of claim 7 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00085## wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.9; and/or ##STR00086##
10. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of: ##STR00087## wherein R.sup.2 is a styrene or C1 to C30 alkyl,
R.sup.3 is a styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1
to C30 alkyl, p, q and y individually range from 0 to up to the
valence of the aryl group to which the respective R groups are
attached.
11. The method of claim 1 wherein the lubricating oil base stock is
present in an amount from about 1 to about 80 weight percent, based
on the total weight of the lubricating oil.
12. The method of claim 1 wherein the at least one monomeric aminic
antioxidant is present in an amount from about 4 to about 8 weight
percent, based on the total weight of the lubricating oil.
13. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is present in an amount from about 0.1
to about 5 weight percent, based on the total weight of the
lubricating oil.
14. The method of claim 1 wherein the formulated oil further
comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
15. The method of claim 14 wherein the other antioxidant comprises
at least one aromatic amine antioxidant, at least one phenolic
antioxidant, or mixtures thereof.
16. The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is formed over time in situ during a
Sequence IIIH engine test in accordance with ASTM D8111-17, or a
General Motors Oxidation and Deposit Test (GMOD) in accordance with
GMW17043, 2.sup.nd Edition, May 2016.
17. The method of claim 1 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO), a commercial vehicle engine
oil (CVEO), or a lubricating oil that is subjected to heat and
oxidative conditions.
18. A method for regenerating at least one oligomeric or polymeric
aminic antioxidant in a lubricating oil, during operation of an
engine or other mechanical component lubricated with the
lubricating oil by using as the lubricating oil a formulated oil,
said formulated oil having a composition comprising a lubricating
oil base stock as a major component; and at least one oligomeric or
polymeric aminic antioxidant and at least one monomeric aminic
antioxidant, as minor components; wherein the at least one
oligomeric or polymeric aminic antioxidant dissipates over time in
the lubricating oil during operation of the engine or other
mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant and the at least one monomeric aminic
antioxidant react to form over time in situ at least one
regenerated oligomeric or polymeric aminic antioxidant during
operation of the engine or other mechanical component; wherein the
lubricating oil base stock is present in an amount from about 1 to
about 95 weight percent, based on the total weight of the
lubricating oil; wherein the at least one oligomeric or polymeric
aminic antioxidant is present in an amount from greater than about
0.1 to about 10 weight percent, based on the total weight of the
lubricating oil; and wherein the at least one monomeric aminic
antioxidant is present in an amount from greater than about 2 to
about 10 weight percent, based on the total weight of the
lubricating oil.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/781,720, filed on Dec. 19, 2018, and is also
related to U.S. Provisional Application No. 62/781,751, filed on
Dec. 19, 2018 the entire contents of which are incorporated herein
by reference.
FIELD
[0002] This disclosure relates to engine lubricating oils with
antioxidant formation and dissipation control. In particular, this
disclosure relates to lubricating oils, and methods for to
controlling formation and dissipation of antioxidants in a
lubricating oil in an engine or other mechanical component
lubricated with the lubricating oil. The lubricating oils of this
disclosure are useful as passenger vehicle engine oil (PVEO)
products, commercial vehicle engine oil (CVEO) products, or other
applications where lubricating oils are subjected to heat and
oxidative conditions.
BACKGROUND
[0003] Lubricant viscosity control is one of the key parameters
affecting oil life, which translates in oil drain interval in
practical terms. Additionally, deposit formation is an issue
associated with the decomposition of the base stock molecules
mostly propagated by oxidative chain reactions. There are several
conventional approaches to improve viscosity control of a finished
lubricant product, including lubricating oil additive packages.
[0004] Improved viscosity control is necessary to increase oil life
and oil drain intervals, thus reducing the amount of used oil
generated as a consequence of more frequent oil changes. Longer oil
life and oil drain intervals are key benefits that are desirable to
end customers. Traditional additive packages provide standard
protection and control leaving the main differentiation hinging on
the quality of the base stock in the formulation.
[0005] What is needed is newly designed lubricants capable of
controlling oil thickening for longer periods of time as compared
to conventional lubricants. Further, what is needed is newly
designed lubricants that enable extended oil life in combination
with desired deposit control and cleanliness performance.
SUMMARY
[0006] This disclosure relates to engine lubricating oils with
antioxidant formation and dissipation control. In particular, this
disclosure relates to lubricating oils, and methods for controlling
formation and dissipation of antioxidants in a lubricating oil in
an engine or other mechanical component lubricated with the
lubricating oil. The lubricating oils of this disclosure are useful
as passenger vehicle engine oil (PVEO) products, commercial vehicle
engine oil (CVEO) products, or other applications where lubricating
oils are subjected to heat and oxidative conditions.
[0007] This disclosure also relates in part to a method for
controlling formation and dissipation of at least one oligomeric or
polymeric aminic antioxidant in a lubricating oil, during operation
of an engine or other mechanical component lubricated with the
lubricating oil by using as the lubricating oil a formulated oil.
The formulated oil has a composition comprising a lubricating oil
base stock as a major component, and at least one oligomeric or
polymeric aminic antioxidant, as a minor component. The at least
one oligomeric or polymeric aminic antioxidant is formed over time
in situ from at least one monomeric aminic antioxidant during
operation of the engine or other mechanical component. The at least
one oligomeric or polymeric aminic antioxidant is dissipated over
time in the lubricating oil during operation of the engine or other
mechanical component. The lubricating oil base stock is present in
an amount from about 1 to about 95 weight percent, based on the
total weight of the lubricating oil, or more preferably from about
1 to about 85 weight percent, based on the total weight of the
lubricating oil, or most preferably from 70 to 95 weight percent,
based on the total weight of the lubricating oil. The at least one
monomeric aminic antioxidant is present in an amount from greater
than about 2 to about 10 weight percent, based on the total weight
of the lubricating oil.
[0008] This disclosure further relates in part to a method for
controlling formation and dissipation of at least one oligomeric or
polymeric aminic antioxidant in a lubricating oil, during operation
of an engine or other mechanical component lubricated with the
lubricating oil by using as the lubricating oil a formulated oil.
The formulated oil has a composition comprising a lubricating oil
base stock as a major component, and at least one monomeric aminic
antioxidant, as a minor component. At least one oligomeric or
polymeric aminic antioxidant is formed over time in situ from the
at least one monomeric aminic antioxidant during operation of the
engine or other mechanical component. The at least one oligomeric
or polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component. The lubricating oil base stock is present in an amount
from about 1 to about 95 weight percent, based on the total weight
of the lubricating oil, or more preferably from about 1 to about 85
weight percent, based on the total weight of the lubricating oil,
or most preferably from 70 to 95 weight percent, based on the total
weight of the lubricating oil. The at least one monomeric aminic
antioxidant is present in an amount from greater than about 2 to
about 10 weight percent, based on the total weight of the
lubricating oil.
[0009] This disclosure yet further relates in part to a method for
controlling formation and dissipation of at least one oligomeric or
polymeric aminic antioxidant in a lubricating oil, during operation
of an engine or other mechanical component lubricated with the
lubricating oil by using as the lubricating oil a formulated oil.
The formulated oil has a composition comprising a lubricating oil
base stock as a major component, and at least one oligomeric or
polymeric aminic antioxidant and at least one monomeric aminic
antioxidant, as minor components. The at least one oligomeric or
polymeric aminic antioxidant and the at least one monomeric aminic
antioxidant react to form over time in situ at least one oligomeric
or polymeric aminic antioxidant reaction product during operation
of the engine or other mechanical component. The at least one
oligomeric or polymeric aminic antioxidant reaction product is
dissipated over time in the lubricating oil during operation of the
engine or other mechanical component. The lubricating oil base
stock is present in an amount from about 1 to about 95 weight
percent, based on the total weight of the lubricating oil, or more
preferably from about 1 to about 85 weight percent, based on the
total weight of the lubricating oil, or most preferably from 70 to
95 weight percent, based on the total weight of the lubricating
oil. The at least one oligomeric or polymeric aminic antioxidant is
present in an amount from greater than about 0.1 to about 10 weight
percent, based on the total weight of the lubricating oil. The at
least one monomeric aminic antioxidant is present in an amount from
greater than about 2 to about 10 weight percent, based on the total
weight of the lubricating oil.
[0010] This disclosure also relates in part to a method for
regenerating at least one oligomeric or polymeric aminic
antioxidant in a lubricating oil, during operation of an engine or
other mechanical component lubricated with the lubricating oil by
using as the lubricating oil a formulated oil. The formulated oil
has a composition comprising a lubricating oil base stock as a
major component, and at least one oligomeric or polymeric aminic
antioxidant and at least one monomeric aminic antioxidant, as minor
components. The at least one oligomeric or polymeric aminic
antioxidant dissipates over time in the lubricating oil during
operation of the engine or other mechanical component. The at least
one oligomeric or polymeric aminic antioxidant and the at least one
monomeric aminic antioxidant react to form over time in situ at
least one regenerated oligomeric or polymeric aminic antioxidant
during operation of the engine or other mechanical component. The
lubricating oil base stock is present in an amount from about 1 to
about 95 weight percent, based on the total weight of the
lubricating oil, or more preferably from about 1 to about 85 weight
percent, based on the total weight of the lubricating oil, or most
preferably from 70 to 95 weight percent, based on the total weight
of the lubricating oil. The at least one oligomeric or polymeric
aminic antioxidant is present in an amount from greater than about
0.1 to about 10 weight percent, based on the total weight of the
lubricating oil. The at least one monomeric aminic antioxidant is
present in an amount from greater than about 2 to about 10 weight
percent, based on the total weight of the lubricating oil.
[0011] This disclosure further relates in part to a lubricating oil
having a composition comprising a lubricating oil base stock as a
major component, and at least one oligomeric or polymeric aminic
antioxidant, as a minor component. In an engine or other mechanical
component lubricated with the lubricating oil, the at least one
oligomeric or polymeric aminic antioxidant is formed over time in
situ from at least one monomeric aminic antioxidant during
operation of the engine or other mechanical component. The at least
one oligomeric or polymeric aminic antioxidant is dissipated over
time in the lubricating oil during operation of the to engine or
other mechanical component. The lubricating oil base stock is
present in an amount from about 1 to about 95 weight percent, based
on the total weight of the lubricating oil, or more preferably from
about 1 to about 85 weight percent, based on the total weight of
the lubricating oil, or most preferably from 70 to 95 weight
percent, based on the total weight of the lubricating oil. The at
least one monomeric aminic antioxidant is present in an amount from
greater than about 2 to about 10 weight percent, based on the total
weight of the lubricating oil.
[0012] This disclosure yet further relates in part to a lubricating
oil having a composition comprising a lubricating oil base stock as
a major component, and at least one monomeric aminic antioxidant,
as a minor component. In an engine or other mechanical component
lubricated with the lubricating oil, at least one oligomeric or
polymeric aminic antioxidant is formed over time in situ from the
at least one monomeric aminic antioxidant during operation of the
engine or other mechanical component. The at least one oligomeric
or polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component. The lubricating oil base stock is present in an amount
from about 1 to about 95 weight percent, based on the total weight
of the lubricating oil, or more preferably from about 1 to about 85
weight percent, based on the total weight of the lubricating oil,
or most preferably from 70 to 95 weight percent, based on the total
weight of the lubricating oil. The at least one monomeric aminic
antioxidant is present in an amount from greater than about 2 to
about 10 weight percent, based on the total weight of the
lubricating oil.
[0013] This disclosure also relates in part to a lubricating oil
having a composition comprising a lubricating oil base stock as a
major component, and at least one oligomeric or polymeric aminic
antioxidant and at least one monomeric aminic antioxidant, as minor
components. In an engine or other mechanical component lubricated
with the lubricating oil, the at least one oligomeric or polymeric
aminic antioxidant and the at least one monomeric aminic
antioxidant react to form over time in situ at least one oligomeric
or polymeric aminic antioxidant reaction product during operation
of the engine or other mechanical component. The at least one
oligomeric or polymeric aminic antioxidant reaction product is
dissipated over time in the lubricating oil during operation of the
engine or other mechanical component. The lubricating oil base
stock is present in an amount from about 1 to about 95 weight
percent, based on the total weight of the lubricating oil, or more
preferably from about 1 to about 85 weight percent, based on the
total weight of the lubricating oil, or most preferably from 70 to
95 weight percent, based on the total weight of the lubricating
oil. The at least one oligomeric or polymeric aminic antioxidant is
present in an amount from greater than about 0.1 to about 10 weight
percent, based on the total weight of the lubricating oil. The at
least one monomeric aminic antioxidant is present in an amount from
greater than about 2 to about 10 weight percent, based on the total
weight of the lubricating oil.
[0014] This disclosure further relates in part to a lubricating oil
having a composition comprising a lubricating oil base stock as a
major component, and at least one oligomeric or polymeric aminic
antioxidant and at least one monomeric aminic antioxidant, as minor
components. In an engine or other mechanical component lubricated
with the lubricating oil, the at least one oligomeric or polymeric
aminic antioxidant dissipates over time in the lubricating oil
during operation of the engine or other mechanical component. the
at least one oligomeric or polymeric aminic antioxidant and the at
least one monomeric aminic antioxidant react to form over time in
situ at least one regenerated oligomeric or polymeric aminic
antioxidant during operation of the engine or other mechanical
component. The lubricating oil base stock is present in an amount
from about 1 to about 95 weight percent, based on the total weight
of the lubricating oil, or more preferably from about 1 to about 85
weight percent, based on the total weight of the lubricating oil,
or most preferably from 70 to 95 weight percent, based on the total
weight of the lubricating oil. The at least one oligomeric or
polymeric aminic antioxidant is present in an amount from greater
than about 0.1 to about 10 weight percent, based on the total
weight of the lubricating oil. The at least one monomeric aminic
antioxidant is present in an amount from greater than about 2 to
about 10 weight percent, based on the total weight of the
lubricating oil.
[0015] It has been surprisingly found that, in accordance with this
disclosure, oligomeric or polymeric aminic antioxidant formation
and dissipation control in lubricating oils is improved using high
treat rates of monomeric aminic antioxidants in lubricating oils,
as compared to oligomeric or polymeric aminic antioxidant formation
and dissipation control in lubricating oils achieved using low
treat rates of monomeric aminic antioxidants in lubricating
oils.
[0016] In particular, it has been surprisingly found that, in
measurements of the lubricating oil by a Sequence IIIH engine test
in accordance with ASTM D8111-17, oligomeric or polymeric aminic
antioxidant formation and dissipation control are improved using a
concentration of monomeric aminic antioxidant from greater than
about 2 to about 10 weight percent, based on the total weight of
the lubricating oil, as compared to oligomeric or polymeric aminic
antioxidant formation and dissipation control achieved using a
lower concentration of the monomeric aminic antioxidant. The
controlled release/in situ generation of oligomeric and polymeric
antioxidants in the lubricating oils, which result from a
concentration of monomeric aminic antioxidant from greater than
about 2 to about 10 weight percent, based on the total weight of
the lubricating oil, leads to surprisingly exceptional performance
in the Sequence IIIH engine test.
[0017] Other objects and advantages of the present disclosure will
become apparent from the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 shows ion counts for oligomers of Irganox.RTM. L57 in
comparative Example 1 formulated oil analyzed by liquid
chromatography mass spectrometry (LCMS).
[0019] FIG. 2 shows ion counts for oligomers of Irganox.RTM. L57 in
inventive Example 2 formulated oil analyzed by LCMS.
DETAILED DESCRIPTION
Definitions
[0020] "About" or "approximately." All numerical values within the
detailed description and the claims herein are modified by "about"
or "approximately" the indicated value, and take into account
experimental error and variations that would be expected by a
person having ordinary skill in the art.
[0021] "Major amount" as it relates to components included within
the lubricating oils of the specification and the claims means
greater than or equal to 50 wt. %, or greater than or equal to 60
wt. %, or greater than or equal to 70 wt. %, or greater than or
equal to 80 wt. %, or greater than or equal to 90 wt. % based on
the total weight of the lubricating oil.
[0022] "Minor amount" as it relates to components included within
the lubricating oils of the specification and the claims means less
than 50 wt. %, or less than or equal to 40 wt. %, or less than or
equal to 30 wt. %, or greater than or equal to 20 wt. %, or less
than or equal to 10 wt. %, or less than or equal to 5 wt. %, or
less than or equal to 2 wt. %, or less than or equal to 1 wt. %,
based on the total weight of the lubricating oil.
[0023] "Essentially free" as it relates to components included
within the lubricating oils of the specification and the claims
means that the particular component is at 0 weight % within the
lubricating oil, or alternatively is at impurity type levels within
the lubricating oil (less than 100 ppm, or less than 20 ppm, or
less than 10 ppm, or less than 1 ppm).
[0024] "Other lubricating oil additives" as used in the
specification and the claims means other lubricating oil additives
that are not specifically recited in the particular section of the
specification or the claims. For example, other lubricating oil
additives may include, but are not limited to, antioxidants,
detergents, dispersants, antiwear additives, corrosion inhibitors,
viscosity modifiers, metal passivators, pour point depressants,
seal compatibility agents, antifoam agents, extreme pressure
agents, friction modifiers and combinations thereof.
[0025] "Other mechanical component" as used in the specification
and the claims means an electric vehicle component, a hybrid
vehicle component, a power train, a driveline, a transmission, a
gear, a gear train, a gear set, a compressor, a pump, a hydraulic
system, a bearing, a bushing, a turbine, a piston, a piston ring, a
cylinder liner, a cylinder, a cam, a tappet, a lifter, a gear, a
valve, or a bearing including a journal, a roller, a tapered, a
needle, and a ball bearing.
[0026] "Hydrocarbon" refers to a compound consisting of carbon
atoms and hydrogen atoms.
[0027] "Alkane" refers to a hydrocarbon that is completely
saturated. An alkane can be linear, branched, cyclic, or
substituted cyclic.
[0028] "Olefin" refers to a non-aromatic hydrocarbon comprising one
or more carbon-carbon double bond in the molecular structure
thereof.
[0029] "Mono-olefin" refers to an olefin comprising a single
carbon-carbon double bond.
[0030] "Cn" group or compound refers to a group or a compound
comprising carbon atoms at total number thereof of n. Thus, "Cm-Cn"
group or compound refers to a group or compound comprising carbon
atoms at a total number thereof in the range from m to n. Thus, a
C1-C50 alkyl group refers to an alkyl group comprising carbon atoms
at a total number thereof in the range from 1 to 50.
[0031] "Carbon backbone" refers to the longest straight carbon
chain in the molecule of the compound or the group in question.
"Branch" refer to any substituted or unsubstituted hydrocarbyl
group connected to the carbon backbone. A carbon atom on the carbon
backbone connected to a branch is called a "branched carbon."
[0032] "Epsilon-carbon" in a branched alkane refers to a carbon
atom in its carbon backbone that is (i) connected to two hydrogen
atoms and two carbon atoms and (ii) connected to a branched carbon
via at least four (4) methylene (CH.sub.2) groups. Quantity of
epsilon carbon atoms in terms of mole percentage thereof in a
alkane material based on the total moles of carbon atoms can be
determined by using, e.g., .sup.13C NMR.
[0033] "Alpha-carbon" in a branched alkane refers to a carbon atom
in its carbon backbone that is with a methyl end with no branch on
the first 4 carbons. It is also measured in mole percentage using
.sup.13C NMR.
[0034] "T/P methyl" in a branched alkane refers to a methyl end and
a methyl in the 2 position. It is also measured in mole percentage
using .sup.13C NMR.
[0035] "P-methyl" in a branched alkane refers to a methyl branch
anywhere on the chain, except in the 2 position. It is also
measured in mole percentage using .sup.13C NMR.
[0036] "SAE" refers to SAE International, formerly known as Society
of Automotive Engineers, which is a professional organization that
sets standards for internal combustion engine lubricating oils.
[0037] "SAE J300" refers to the viscosity grade classification
system of engine lubricating oils established by SAE, which defines
the limits of the classifications in rheological terms only.
[0038] "Base stock" or "base oil" interchangeably refers to an oil
that can be used as a component of lubricating oils, heat transfer
oils, hydraulic oils, grease products, and the like.
[0039] "Lubricating oil" or "lubricant" interchangeably refers to a
substance that can be introduced between two or more surfaces to
reduce the level of friction between two adjacent surfaces moving
relative to each other. A lubricant base stock is a material,
typically a fluid at various levels of viscosity at the operating
temperature of the lubricant, used to formulate a lubricant by
admixing with other components. Non-limiting examples of base
stocks suitable in lubricants include API Group I, Group II, Group
III, Group IV, and Group V base stocks. PAOs, particularly
hydrogenated PAOs, have recently found wide use in lubricants as a
Group IV base stock, and are particularly preferred. If one base
stock is designated as a primary base stock in the lubricant,
additional base stocks may be called a co-base stock.
[0040] All kinematic viscosity values in this disclosure are as
determined pursuant to ASTM D445. Kinematic viscosity at
100.degree. C. is reported herein as KV100, and kinematic viscosity
at 40.degree. C. is reported herein as KV40. Unit of all KV100 and
KV40 values herein is cSt unless otherwise specified. When
describing the kinematic viscosity at 100.degree. C. is
"essentially" maintained, the kinematic viscosity at 100.degree. C.
is expected to vary less than 0.2 cSt as measured by ASTM D445.
[0041] All viscosity index ("VI") values in this disclosure are as
determined pursuant to ASTM D2270.
[0042] All Noack volatility ("NV") values in this disclosure are as
determined pursuant to ASTM D5800 unless specified otherwise. Unit
of all NV values is wt %, unless otherwise specified.
[0043] All pour point values in this disclosure are as determined
pursuant to ASTM D5950 or D97.
[0044] All CCS viscosity ("CCSV") values in this disclosure are as
determined pursuant to ASTM 5293. Unit of all CCSV values herein is
millipascal second (mPas), which is equivalent to centipoise),
unless specified otherwise. All CCSV values are measured at a
temperature of interest to the lubricating oil formulation or oil
composition in question. Thus, for the purpose of designing and
fabricating engine oil formulations, the temperature of interest is
the temperature at which the SAE J300 imposes a minimal CCSV.
[0045] All percentages in describing chemical compositions herein
are by weight unless specified otherwise. "Wt.%" means percent by
weight.
Lubricating Oil Compositions of This Disclosure
[0046] This disclosure describes the controlled in situ generation
of powerful oligomeric or polymeric antioxidants in the engine of a
passenger vehicle, commercial vehicle, a fired engine, or other
mechanical component.
[0047] Antioxidants are critical to delivering viscosity control
over the entire oil drain interval. This disclosure describes the
in situ generation of oligomeric and polymeric antioxidants from
conventional monomeric aminic antioxidants during normal engine
use. This disclosure also describes the controlled in situ
regeneration of commercial oligomeric and polymeric antioxidants
during engine use, by co-formulating them in situ with conventional
aminic antioxidants.
[0048] Further, in accordance with this disclosure, finished
lubricants can be designed with in situ generated oligomeric and
polymeric antioxidants that are capable of controlling oil
thickening for long durations as compared to conventional
lubricants. This disclosure also enables extended oil life in
combination with superior deposit control and cleanliness
performance through the in situ generation of oligomeric and
polymeric antioxidants.
[0049] This disclosure describes the superior performance of
conventional monomeric aminic antioxidants in lubricating oils. It
also allows for the in situ production of oligomeric and polymeric
antioxidants from the monomeric aminic antioxidants during engine
use. It further allows for a reduction of the treat rate of the
oligomeric and polymeric antioxidants, replacing the balance with
traditional monomeric aminic antioxidants which can react in situ
to form oligomeric and polymeric antioxidants and which come at a
lower cost and result in a more acceptable formulation
appearance/color.
[0050] In general, formulators use low treat rates of aminic
antioxidants (<2 wt %, and often less than 1 wt %) such as
Irganox L57 or Irganox L67 in passenger vehicle formulations. In
accordance with this disclosure, it has been found that at a high
enough treat rate (5 wt % for example), monomeric aminic
antioxidants can form analogous oligomers and polymers during the
course of a Sequence IIIH engine test resulting in superior
performance in respect to viscosity control (see FIG. 1) and
cleanliness (see FIG. 2).
[0051] In measurements of the lubricating oil by a Sequence IIIH
engine test in accordance with ASTM D8111-17, oligomeric or
polymeric aminic antioxidant formation and dissipation control are
improved using high treat rates (e.g., 5 wt %) of monomeric aminic
antioxidants as compared to oligomeric or polymeric aminic
antioxidant formation and dissipation control achieved using low
treat rates (e.g., 2 wt %) of monomeric aminic antioxidants. The
controlled release/in situ generation of oligomeric and polymeric
antioxidants in the lubricating oils, which result from the high
treat rates (e.g., 5 wt %) of monomeric aminic antioxidants, leads
to exceptional performance in the Sequence IIIH engine test.
Lubricating Oil Base Stocks
[0052] A wide range of lubricating base oils is known in the art.
Lubricating base oils that are useful in the present disclosure are
both natural oils, and synthetic oils, and unconventional oils (or
mixtures thereof) can be used unrefined, refined, or rerefined (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. Rerefined oils are
obtained by processes analogous to refined oils but using an oil
that has been previously used as a feed stock.
[0053] 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 between about 80 to 120 and contain greater than about 0.03%
sulfur and/or less than about 90% saturates. Group II base stocks
have a viscosity index of between about 80 to 120, and contain less
than or equal to about 0.03% sulfur and greater than or equal to
about 90% saturates. Group III stocks have a viscosity index
greater than about 120 and contain less than or equal to about
0.03% sulfur and greater than about 90% saturates. Group IV
includes polyalphaolefins (PAO). Group V base stock includes base
stocks not included in Groups I-IV. The table below summarizes
properties of each of these five groups.
TABLE-US-00001 Base Oil Properties Saturates Sulfur Viscosity Index
Group I <90 and/or >0.03% and .gtoreq.80 and <120 Group II
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.80 and <120 Group III
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.120 Group IV
Polyalphaolefins (PAO) Group V All other base oil stocks not
included in Groups I, II, III or IV
[0054] 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.
Of the natural oils, mineral oils are preferred. 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.
[0055] 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.
[0056] 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.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.
[0057] 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
about 250 to about 3,000, although PAO's may be made in viscosities
up to about 150 cSt (100.degree. C.). The PAOs are typically
comprised of relatively low molecular weight hydrogenated polymers
or oligomers of alphaolefins which include, but are not limited to,
C.sub.2 to about C.sub.32 alphaolefins with the C.sub.8 to about
C.sub.16 alphaolefins, such as 1-hexene, 1-octene, 1-decene,
1-dodecene and the like, being preferred. The preferred
polyalphaolefins are 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
C.sub.14 to C.sub.18 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 150 cSt may be used if
desired.
[0058] 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 to 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 C.sub.14 to C.sub.18
olefins are described in U.S. Pat. No. 4,218,330.
[0059] The alkylated naphthalene can be used as base oil or base
oil component and can be any hydrocarbyl molecule that contains at
least about 5% of its weight derived from a naphthenoid moiety, or
its derivatives. These alkylated naphthalenes include alkyl
naphthalenes, alkyl naphthols, and the like. The naphthenoid group
can be mono-alkylated, dialkylated, polyalkylated, and the like.
The naphthenoid group can be mono- or poly-functionalized. The
naphthenoid group can also be derived from natural (petroleum)
sources, provided at least about 5% of the molecule is comprised of
the naphthenoid moiety. Viscosities at 100.degree. C. of
approximately 3 cSt to about 50 cSt are preferred, with viscosities
of approximately 3.4 cSt to about 20 cSt often being more preferred
for the naphthylene component. In one embodiment, an alkyl
naphthalene where the alkyl group is primarily comprised of
1-hexadecene is used. Other alkylates of naphthalene 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.
[0060] Alkylated naphthalenes 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 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
AlCl.sub.3, BF.sub.3, or HF may be used. In some cases, milder
catalysts such as FeCl.sub.3 or SnCl.sub.4 are preferred. Newer
alkylation technology uses zeolites or solid super acids.
[0061] Mixtures of alkylated naphthalene base stocks with other
lubricating oil base stocks (e.g., Groups I, II, III, IV and V base
stocks) may be useful in the lubricating oil formulations of this
disclosure.
[0062] The alkylated naphthalene can be present in an amount of
from about 30 to about 99.8 weight percent, or from about 35 to
about 95 weight percent, or from about 40 to about 90 weight
percent, or from about 45 to about 85 weight percent, or from about
50 to about 80 weight percent, or from about 55 to about 75 weight
percent, or from about 60 to about 70 weight percent, based on the
total weight of the formulated oil.
[0063] Other useful lubricant oil base stocks 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, preferably a zeolitic
catalyst. For example, one useful catalyst is ZSM-48 as described
in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated
herein by reference in its entirety. 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. Each of the aforementioned patents is incorporated
herein in their entirety. 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, the disclosures of which are incorporated herein by
reference in their entirety.
[0064] 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 about 3 cSt
to about 50 cSt, preferably about 3 cSt to about 30 cSt, more
preferably about 3.5 cSt to about 25 cSt, as exemplified by GTL 4
with kinematic viscosity of about 4.0 cSt at 100.degree. C. and a
viscosity index of about 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 about
-20.degree. C. or lower, and under some conditions may have
advantageous pour points of about -25.degree. C. or lower, with
useful pour points of about -30.degree. C. to about -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 in U.S. Pat. Nos. 6,080,301;
6,090,989, and 6,165,949 for example, and are incorporated herein
in their entirety by reference.
[0065] The hydrocarbyl aromatics can be used as base oil or base
oil component and can be to any hydrocarbyl molecule that contains
at least about 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 about C.sub.6 up to about
C.sub.60 with a range of about C.sub.8 to about C.sub.20 often
being preferred. A mixture of hydrocarbyl groups is often
preferred, and up to about three such substituents may be present.
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 about
5% of the molecule is comprised of an above-type aromatic moiety.
Viscosities at 100.degree. C. of approximately 3 cSt to about 50
cSt are preferred, with viscosities of approximately 3.4 cSt to
about 20 cSt often being more preferred for the hydrocarbyl
aromatic component. 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 about 2% to about 25%, preferably about 4% to
about 20%, and more preferably about 4% to about 15%, depending on
the application.
[0066] 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 AlCl.sub.3,
BF.sub.3, or HF may be used. In some cases, milder catalysts such
as FeCl.sub.3 or SnCl.sub.4 are preferred. Newer alkylation
technology uses zeolites or solid super acids.
[0067] Other useful fluids of lubricating viscosity include
non-conventional or unconventional base stocks that have been
processed, preferably catalytically, or synthesized to provide high
performance lubrication characteristics.
[0068] Non-conventional or unconventional 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.
[0069] 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.
[0070] 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); preferably 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.
[0071] 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, preferably 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 -5.degree. C. to about -40.degree. C. or lower (ASTM
D97). They are also characterized typically as having viscosity
indices of about 80 to about 140 or greater (ASTM D2270).
[0072] 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) typically have very low sulfur and
nitrogen content, generally containing less than about 10 ppm, and
more typically less than about 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
materially especially suitable for the formulation of low SAP
products.
[0073] 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.
[0074] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived is preferably an F-T material (i.e.,
hydrocarbons, waxy hydrocarbons, wax).
[0075] 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 II, Group III, Group IV, and
Group V oils and mixtures thereof, preferably API Group II, Group
III, Group IV, and Group V oils and mixtures thereof, more
preferably the Group III to Group V base oils due to their
exceptional volatility, stability, viscometric and cleanliness
features.
[0076] This other base oil typically is present in an amount
ranging from about 0.1 to about 90 weight percent, or from about 1
to about 80 weight percent, or from about 1 to about 70 weight
percent, or from about 1 to about 60 weight percent, or from about
1 to about 50 weight percent, based on the total weight of the
composition. The base oil may be selected from any of the synthetic
or natural oils typically used as crankcase lubricating oils for
spark ignition and compression-ignited engines. The base oil
conveniently has a kinematic viscosity, according to ASTM
standards, of about 2.5 cSt to about 12 cSt (or mm.sup.2/s) at
100.degree. C. and preferably of about 2.5 cSt to about 9 cSt (or
mm.sup.2/s) at 100.degree. C. Mixtures of synthetic and natural
base oils may be used if desired. Mixtures of Group III, IV, and V
may be preferable.
Oligomeric and Polymeric Aminic Antioxidants
[0077] Illustrative oligomeric and polymeric aminic antioxidants
include oligomerization and polymerization reaction products of one
or more unsubstituted or hydrocarbyl-substituted diphenyl amines,
one or more unsubstituted or hydrocarbyl-substituted phenyl
naphthyl amines or both one or more of unsubstituted or
hydrocarbyl-substituted diphenylamine with one or more
unsubstituted or hydrocarbyl-substituted phenyl naphthylamine. A
representative schematic is presented below:
##STR00001##
wherein (A) and (B) each range from zero to 10, preferably zero to
5, more preferably zero to 3, most preferably 1 to 3, provided
(A)+(B) is at least 2; R.sup.2 is a styrene or C1 to C30 alkyl,
R.sup.3 is a styrene or C1 to C30 alkyl, q and y individually range
from 0 to up to the valence of the aryl group to which the
respective R groups are attached; for example:
##STR00002##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, preferably R.sup.2 is a C1 to C30 alkyl, R.sup.3 is a C1 to
C30 alkyl, R.sup.4 is a C1 to C30 alkyl, more preferably R.sup.2 is
a C4 to C10 alkyl, R.sup.3 is a C4 to C10 alkyl and R.sup.4 is a C4
to C10 alkyl, p, q and y individually range from 0 to up to the
valence of the aryl group to which the respective R groups are
attached, preferably at least one of p, q and y range from 1 to up
to the valence of the aryl group to which the respective R group(s)
are attached, more preferably p, q and y each individually range
from at least 1 to up to the valence of the aryl group to which the
respective R groups are attached.
[0078] In a preferred embodiment, the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of (A)
and (B) above including, but not limited to, (A)(A), (A)(B),
(B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A) (A)(B)(B)(B)(A), and
the like.
[0079] In another preferred embodiment, the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00003##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or C.sub.4H.sub.9;
and/or
##STR00004##
[0080] In a further preferred embodiment, the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product formed by any combination
of:
##STR00005##
[0081] In yet a further preferred embodiment, the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product formed by any combination
of:
##STR00006##
[0082] Other more extensive oligomers and polymers are within the
scope of this disclosure, but materials of formulae (a), (b), (c)
and (d) are preferred.
[0083] The oligomeric or polymeric aminic antioxidant may contain
nonpolymerized aryl amine antioxidant starting materials as a
result of the preparation procedure. Additional monomeric amine
antioxidants may be added to the lubricant to impart desired
properties. Examples of monomeric amine antioxidants include but
are not limited to diphenyl amine, alkylated diphenyl amines,
styrenated diphenyl amines, phenyl-N-naphthyl amine, alkylated
phenyl-N-naphthyl amines, styrenated phenyl-N-naphthyl amines,
phenothiazine, alkylated phenothiazine, and styrenated
phenothiazine. Other antioxidants such as hindered phenols and zinc
dithiophosphates can also be added to the lubricant in addition to
the polymerized amine antioxidant.
[0084] The oligomeric and polymeric aminic antioxidants useful in
this disclosure can be prepared by conventional polymerization
reactions. See, for example, U.S. Pat. Nos. 6,426,324 and
8,623,795. An illustrative polymerization reaction for preparing
preferred oligomeric and polymeric aminic antioxidants useful in
this disclosure is set forth below. The product of the reaction can
yield more than the two oligomers shown below, for example, any
combination of (A) and (B) below including, but not limited to,
(A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B),
(B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A),
and the like.
##STR00007##
[0085] The oligomeric or polymeric aminic antioxidant is present in
an amount in the range 0.1 to 10 wt % (active ingredient),
preferably 0.1 to 5 wt % (active ingredient), or 0.1 to 4 wt %
(active ingredient), or 0.1 to 2.5 wt % (active ingredient) or 0.1
to 1.5 wt % (active ingredient), or to 1.5 to 4 wt % (active
ingredient), of oligomerized or polymerized aminic antioxidant
exclusive of any added antioxidants.
Monomeric Aminic Antioxidants
[0086] Illustrative monomeric aminic antioxidants useful in this
disclosure include one or more unsubstituted or
hydrocarbyl-substituted diphenyl amines, one or more unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amines or both one or
more of unsubstituted or hydrocarbyl-substituted diphenylamine and
one or more unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
[0087] Preferred monomeric aminic antioxidants useful in this
disclosure include:
##STR00008##
[0088] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00009##
[0089] In a further preferred embodiment, the at least one
monomeric aminic antioxidant can include:
##STR00010##
[0090] In yet a further preferred embodiment, the at least one
monomeric aminic antioxidant can include:
##STR00011##
[0091] Additional monomeric amine antioxidants may be added to the
lubricant to impart desired properties. Examples of monomeric amine
antioxidants include but are not limited to diphenyl amine,
alkylated diphenyl amines, styrenated diphenyl amines,
phenyl-N-naphthyl amine, alkylated phenyl-N-naphthyl amines,
styrenated phenyl-N-naphthyl amines, phenothiazine, alkylated
phenothiazine, and styrenated phenothiazine.
[0092] Monomeric amine antioxidants include unsubstituted or
hydrocarbon-substituted diphenyl amines, unsubstituted or
hydrocarbyl-substituted phenyl naphthyl amines and unsubstituted or
hydrocarbyl-substituted phenothiazines wherein the
hydrocarbyl-substituted to group is styrene or a C1 to C30 alkyl
group, preferably a C1 to C10 alkyl group, more preferably a C4 to
C10 alkyl group. Other monomeric aryl amines have been described in
the patent literature.
[0093] The monomeric aminic antioxidants useful in this disclosure
can be prepared by conventional polymerization reactions. See, for
example, U.S. Pat. Nos. 6,426,324 and 8,623,795.
[0094] The monomeric aminic antioxidant is present in an amount in
the range 0.1 to 10 wt % (active ingredient), preferably 0.1 to 8
wt % (active ingredient), or 0.1 to 7.5 wt % (active ingredient),
or 0.1 to 5 wt % (active ingredient) or 0.1 to 2.5 wt % (active
ingredient), or 1.5 to 5 wt % (active ingredient), of monomeric
aminic antioxidant exclusive of any added antioxidants.
[0095] Preferably, the monomeric aminic antioxidant is present in
an amount in the range greater than about 2 to 10 wt % (active
ingredient), preferably 2.5 to 9.5 wt % (active ingredient), or 3
to 9 wt % (active ingredient), or 3.5 to 8.5 wt % (active
ingredient), or 4 to 8 wt % (active ingredient), or 4.5 to 7.5 wt %
(active ingredient), or 5 to 7 wt % (active ingredient), or 5 to 6
wt % (active ingredient), of monomeric aminic antioxidant exclusive
of any added antioxidants.
Other Additives
[0096] The formulated lubricating oil useful in the present
disclosure may additionally contain one or more of the other
commonly used lubricating oil performance additives including but
not limited to dispersants, detergents, other antioxidants,
antiwear additives, 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, defoamants, demulsifiers, emulsifiers, densifiers, wetting
agents, gelling agents, tackiness agents, colorants, and others.
For a review of many commonly used additives, see Klamann in
Lubricants and Related Products, Verlag Chemie, Deerfield Beach,
Fla.; ISBN 0-89573-177-0. Reference is also made to "Lubricant
Additives" by M. W. Ranney, published by Noyes Data Corporation of
Parkridge, N J (1973); see also U.S. Pat. No. 7,704,930, the
disclosure of which is incorporated herein in its entirety. These
additives are commonly delivered with varying amounts of diluent
oil, that may range from 5 weight percent to 50 weight percent.
Dispersants
[0097] During engine operation, oil-insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposition on metal surfaces. Dispersants
used in the formulation of the lubricating oil may be ashless or
ash-forming in nature. Preferably, the dispersant is ashless. So
called ashless dispersants are organic materials that form
substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents
discussed above form ash upon combustion.
[0098] Suitable dispersants typically contain a polar group
attached to a relatively high molecular weight hydrocarbon chain.
The polar group typically contains at least one element of
nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain
50 to 400 carbon atoms.
[0099] A particularly useful class of dispersants are the
(poly)alkenylsuccinic derivatives, typically produced by the
reaction of a long chain hydrocarbyl substituted succinic compound,
usually a hydrocarbyl substituted succinic anhydride, with a
polyhydroxy or polyamino compound. The long chain hydrocarbyl group
constituting the oleophilic portion of the molecule which confers
solubility in the oil, is normally a polyisobutylene group. Many
examples of this type of dispersant are well known commercially and
in the literature. Exemplary U.S. patents describing such
dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707; 3,219,666;
3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904;
3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are
described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;
3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;
3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;
3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A
further description of dispersants may be found, for example, in
European Patent Application No. 471 071, to which reference is made
for this purpose.
[0100] Hydrocarbyl-substituted succinic acid and
hydrocarbyl-substituted succinic anhydride derivatives are useful
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound preferably having at
least 50 carbon atoms in the hydrocarbon substituent, with at least
one equivalent of an alkylene amine are particularly useful.
[0101] Succinimides are formed by the condensation reaction between
hydrocarbyl substituted succinic anhydrides and amines. Molar
ratios can vary depending on the polyamine. For example, the molar
ratio of hydrocarbyl substituted succinic anhydride to TEPA can
vary from about 1:1 to about 5:1. Representative examples are shown
in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746;
3,322,670; and 3,652,616, 3,948,800; and Canada Patent No.
1,094,044.
[0102] Succinate esters are formed by the condensation reaction
between hydrocarbyl substituted succinic anhydrides and alcohols or
polyols. Molar ratios can vary depending on the alcohol or polyol
used. For example, the condensation product of a hydrocarbyl
substituted succinic anhydride and pentaerythritol is a useful
dispersant.
[0103] Succinate ester amides are formed by condensation reaction
between hydrocarbyl substituted succinic anhydrides and alkanol
amines. For example, suitable alkanol amines include ethoxylated
polyalkylpolyamines, propoxylated polyalkylpolyamines and
polyalkenylpolyamines such as polyethylene polyamines. One example
is propoxylated hexamethylenediamine. Representative examples are
shown in U.S. Pat. No. 4,426,305.
[0104] The molecular weight of the hydrocarbyl substituted succinic
anhydrides used in the preceding paragraphs will typically range
between 800 and 2,500 or more. The above products can be
post-reacted with various reagents such as sulfur, oxygen,
formaldehyde, carboxylic acids such as oleic acid. The above
products can also be post reacted with boron compounds such as
boric acid, borate esters or highly borated dispersants, to form
borated dispersants generally having from about 0.1 to about 5
moles of boron per mole of dispersant reaction product.
[0105] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See U.S. Pat. No.
4,767,551, which is incorporated herein by reference. Process aids
and catalysts, such as oleic acid and sulfonic acids, can also be
part of the reaction mixture. Molecular weights of the alkylphenols
range from 800 to 2,500. Representative examples are shown in U.S.
Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953;
3,798,165; and 3,803,039.
[0106] Typical high molecular weight aliphatic acid modified
Mannich condensation products useful in this disclosure can be
prepared from high molecular weight alkyl-substituted
hydroxyaromatics or HNR.sub.2 group-containing reactants.
[0107] Hydrocarbyl substituted amine ashless dispersant additives
are well known to one skilled in the art; see, for example, U.S.
Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209,
and 5,084,197.
[0108] Preferred dispersants include borated and non-borated
succinimides, including those derivatives from mono-succinimides,
bis-succinimides, and/or mixtures of mono- and bis-succinimides,
wherein the hydrocarbyl succinimide is derived from a
hydrocarbylene group such as polyisobutylene having a Mn of from
about 500 to about 5000, or from about 1000 to about 3000, or about
1000 to about 2000, or a mixture of such hydrocarbylene groups,
often with high terminal vinylic groups. Other preferred
dispersants include succinic acid-esters and amides,
alkylphenol-polyamine-coupled Mannich adducts, their capped
derivatives, and other related components.
[0109] Polymethacrylate or polyacrylate derivatives are another
class of dispersants. These dispersants are typically prepared by
reacting a nitrogen containing monomer and a methacrylic or acrylic
acid esters containing 5-25 carbon atoms in the ester group.
Representative examples are shown in U.S. Pat. Nos. 2,100,993, and
6,323,164. Polymethacrylate and polyacrylate dispersants are
normally used as multifunctional viscosity modifiers. The lower
molecular weight versions can be used as lubricant dispersants or
fuel detergents.
[0110] Illustrative preferred dispersants useful in this disclosure
include those derived from polyalkenyl-substituted mono- or
dicarboxylic acid, anhydride or ester, which dispersant has a
polyalkenyl moiety with a number average molecular weight of at
least 900 and from greater than 1.3 to 1.7, preferably from greater
than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5,
functional groups (mono- or dicarboxylic acid producing moieties)
per polyalkenyl moiety (a medium functionality dispersant).
Functionality (F) can be determined according to the following
formula:
F=(SAP.times.M.sub.n)/((112,200.times.A.I.)-(SAP.times.98))
wherein SAP is the saponification number (i.e., the number of
milligrams of KOH consumed in the complete neutralization of the
acid groups in one gram of the succinic-containing reaction
product, as determined according to ASTM D94); M.sub.n is the
number average molecular weight of the starting olefin polymer; and
A.I. is the percent active ingredient of the succinic-containing
reaction product (the remainder being unreacted olefin polymer,
succinic anhydride and diluent).
[0111] The polyalkenyl moiety of the dispersant may have a number
average molecular weight of at least 900, suitably at least 1500,
preferably between 1800 and 3000, such as between 2000 and 2800,
more preferably from about 2100 to 2500, and most preferably from
about 2200 to about 2400. The molecular weight of a dispersant is
generally expressed in terms of the molecular weight of the
polyalkenyl moiety. This is because the precise molecular weight
range of the dispersant depends on numerous parameters including
the type of polymer used to derive the dispersant, the number of
functional groups, and the type of nucleophilic group employed.
[0112] Polymer molecular weight, specifically M.sub.n, can be
determined by various known techniques. One convenient method is
gel permeation chromatography (GPC), which additionally provides
molecular weight distribution information (see W. W. Yau, J. J.
Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography", John Wiley and Sons, New York, 1979). Another
useful method for determining molecular weight, particularly for
lower molecular weight polymers, is vapor pressure osmometry (e.g.,
ASTM D3592).
[0113] The polyalkenyl moiety in a dispersant preferably has a
narrow molecular weight distribution (MWD), also referred to as
polydispersity, as determined by the ratio of weight average
molecular weight (M.sub.w) to number average molecular weight
(M.sub.n). Polymers having a M.sub.w/M.sub.n of less than 2.2,
preferably less than 2.0, are most desirable. Suitable polymers
have a polydispersity of from about 1.5 to 2.1, preferably from
about 1.6 to about 1.8.
[0114] Suitable polyalkenes employed in the formation of the
dispersants include homopolymers, interpolymers or lower molecular
weight hydrocarbons. One family of such polymers comprise polymers
of ethylene and/or at least one C.sub.3 to C.sub.2 alpha-olefin
having the formula H.sub.2C.dbd.CHR.sup.1 wherein R.sup.1 is a
straight or branched chain alkyl radical comprising 1 to 26 carbon
atoms and wherein the polymer contains carbon-to-carbon
unsaturation, and a high degree of terminal ethenylidene
unsaturation. Preferably, such polymers comprise interpolymers of
ethylene and at least one alpha-olefin of the above formula,
wherein R.sup.1 is alkyl of from 1 to 18 carbon atoms, and more
preferably is alkyl of from 1 to 8 carbon atoms, and more
preferably still of from 1 to 2 carbon atoms.
[0115] Another useful class of polymers is polymers prepared by
cationic polymerization of monomers such as isobutene and styrene.
Common polymers from this class include polyisobutenes obtained by
polymerization of a C.sub.4 refinery stream having a butene content
of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt. A
preferred source of monomer for making poly-n-butenes is petroleum
feed streams such as Raffinate II. These feed stocks are disclosed
in the art such as in U.S. Pat. No. 4,952,739. A preferred
embodiment utilizes polyisobutylene prepared from a pure
isobutylene stream or a Raffinate I stream to prepare reactive
isobutylene polymers with terminal vinylidene olefins.
Polyisobutene polymers that may be employed are generally based on
a polymer chain of from 1500 to 3000.
[0116] The dispersant(s) are preferably non-polymeric (e.g., mono-
or bis-succinimides). Such dispersants can be prepared by
conventional processes such as disclosed in U.S. Patent Application
Publication No. 2008/0020950, the disclosure of which is
incorporated herein by reference.
[0117] The dispersant(s) can be borated by conventional means, as
generally disclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and
5,430,105.
[0118] Such dispersants may be used in an amount of about 0.01 to
20 weight percent or 0.01 to 10 weight percent, preferably about
0.5 to 8 weight percent, or more preferably 0.5 to 4 weight
percent. Or such dispersants may be used in an amount of about 2 to
12 weight percent, preferably about 4 to 10 weight percent, or more
preferably 6 to 9 weight percent. On an active ingredient basis,
such additives may be used in an amount of about 0.06 to 14 weight
percent, preferably about 0.3 to 6 weight percent. The hydrocarbon
portion of the dispersant atoms can range from C.sub.60 to
C.sub.1000, or from C.sub.70 to C.sub.300, or from C.sub.70 to
C.sub.200. These dispersants may contain both neutral and basic
nitrogen, and mixtures of both. Dispersants can be end-capped by
borates and/or cyclic carbonates. Nitrogen content in the finished
oil can vary from about 200 ppm by weight to about 2000 ppm by
weight, preferably from about 200 ppm by weight to about 1200 ppm
by weight. Basic nitrogen can vary from about 100 ppm by weight to
about 1000 ppm by weight, preferably from about 100 ppm by weight
to about 600 ppm by weight.
[0119] Dispersants as described herein are beneficially useful with
the compositions of this disclosure and substitute for some or all
of the surfactants of this disclosure. Further, in one embodiment,
preparation of the compositions of this disclosure using one or
more dispersants is achieved by combining ingredients of this
disclosure, plus optional base stocks and lubricant additives, in a
mixture at a temperature above the melting point of such
ingredients, particularly that of the one or more M-carboxylates
(M=H, metal, two or more metals, mixtures thereof).
[0120] As used herein, the dispersant concentrations are given on
an "as delivered" basis. Typically, the active dispersant is
delivered with a process oil. The "as delivered" dispersant
typically contains from about 20 weight percent to about 80 weight
percent, or from about 40 weight percent to about 60 weight
percent, of active dispersant in the "as delivered" dispersant
product.
Detergents
[0121] Illustrative detergents useful in this disclosure include,
for example, alkali metal detergents, alkaline earth metal
detergents, or mixtures of one or more alkali metal detergents and
one or more alkaline earth metal detergents. A typical detergent is
an anionic material that contains a long chain hydrophobic portion
of the molecule and a smaller anionic or oleophobic hydrophilic
portion of the molecule. The anionic portion of the detergent is
typically derived from an organic acid such as a sulfur-containing
acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing
acid, phenol, or mixtures thereof. The counterion is typically an
alkaline earth or alkali metal. The detergent can be overbased as
described herein.
[0122] The detergent is preferably a metal salt of an organic or
inorganic acid, a metal salt of a phenol, or mixtures thereof. The
metal is preferably selected from an alkali metal, an alkaline
earth metal, and mixtures thereof. The organic or inorganic acid is
selected from an aliphatic organic or inorganic acid, a
cycloaliphatic organic or inorganic acid, an aromatic organic or
inorganic acid, and mixtures thereof.
[0123] The metal is preferably selected from an alkali metal, an
alkaline earth metal, and mixtures thereof. More preferably, the
metal is selected from calcium (Ca), magnesium (Mg), and mixtures
thereof.
[0124] The organic acid or inorganic acid is preferably selected
from a sulfur-containing acid, a carboxylic acid, a
phosphorus-containing acid, and mixtures thereof.
[0125] Preferably, the metal salt of an organic or inorganic acid
or the metal salt of a phenol comprises calcium phenate, calcium
sulfonate, calcium salicylate, magnesium phenate, magnesium
sulfonate, magnesium salicylate, an overbased detergent, and
mixtures thereof.
[0126] Salts that contain a substantially stochiometric amount of
the metal are described as neutral salts and have a total base
number (TBN, as measured by ASTM D2896) of from 0 to 80. Many
compositions are overbased, containing large amounts of a metal
base that is achieved by reacting an excess of a metal compound (a
metal hydroxide or oxide, for example) with an acidic gas (such as
carbon dioxide). Useful detergents can be neutral, mildly
overbased, or highly overbased. These detergents can be used in
mixtures of neutral, overbased, highly overbased calcium
salicylate, sulfonates, phenates and/or magnesium salicylate,
sulfonates, phenates. The TBN ranges can vary from low, medium to
high TBN products, including as low as 0 to as high as 600.
Preferably the TBN delivered by the detergent is between 1 and 20.
More preferably between 1 and 12. Mixtures of low, medium, high TBN
can be used, along with mixtures of calcium and magnesium metal
based detergents, and including sulfonates, phenates, salicylates,
and carboxylates. A detergent mixture with a metal ratio of 1, in
conjunction of a detergent with a metal ratio of 2, and as high as
a detergent with a metal ratio of 5, can be used. Borated
detergents can also be used.
[0127] Alkaline earth phenates are another useful class of
detergent. These detergents can be made by reacting alkaline earth
metal hydroxide or oxide (CaO, Ca(OH).sub.2, BaO, Ba(OH).sub.2,
MgO, Mg(OH).sub.2, for example) with an alkyl phenol or sulfurized
alkylphenol. Useful alkyl groups include straight chain or branched
C.sub.1-C.sub.30 alkyl groups, preferably, C.sub.4-C.sub.20 or
mixtures thereof. Examples of suitable phenols include
isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol,
and the like. It should be noted that starting alkylphenols may
contain more than one alkyl substituent that are each independently
straight chain or branched and can be used from 0.5 to 6 weight
percent. When a non-sulfurized alkylphenol is used, the sulfurized
product may be obtained by methods well known in the art. These
methods include heating a mixture of alkylphenol and sulfurizing
agent (including elemental sulfur, sulfur halides such as sulfur
dichloride, and the like) and then reacting the sulfurized phenol
with an alkaline earth metal base.
[0128] In accordance with this disclosure, metal salts of
carboxylic acids are preferred detergents. These carboxylic acid
detergents may be prepared by reacting a basic metal compound with
at least one carboxylic acid and removing free water from the
reaction product. These compounds may be overbased to produce the
desired TBN level. Detergents made from salicylic acid are one
preferred class of detergents derived from carboxylic acids. Useful
salicylates include long chain alkyl salicylates. One useful family
of compositions is of the formula
##STR00012##
where R is an alkyl group having 1 to about 30 carbon atoms, n is
an integer from 1 to 4, and M is an alkaline earth metal. Preferred
R groups are alkyl chains of at least C.sub.11, preferably C.sub.13
or greater. R may be optionally substituted with substituents that
do not interfere with the detergent's function. M is preferably,
calcium, magnesium, barium, or mixtures thereof. More preferably, M
is calcium.
[0129] Hydrocarbyl-substituted salicylic acids may be prepared from
phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). The
metal salts of the hydrocarbyl-substituted salicylic acids may be
prepared by double decomposition of a metal salt in a polar solvent
such as water or alcohol.
[0130] Alkaline earth metal phosphates are also used as detergents
and are known in the art.
[0131] Detergents may be simple detergents or what is known as
hybrid or complex detergents. The latter detergents can provide the
properties of two detergents without the need to blend separate
materials. See U.S. Pat. No. 6,034,039.
[0132] Preferred detergents include calcium sulfonates, magnesium
sulfonates, calcium salicylates, magnesium salicylates, calcium
phenates, magnesium phenates, and other related components
(including borated detergents), and mixtures thereof. Preferred
mixtures of detergents include magnesium sulfonate and calcium
salicylate, magnesium sulfonate and calcium sulfonate, magnesium
sulfonate and calcium phenate, calcium phenate and calcium
salicylate, calcium phenate and calcium sulfonate, calcium phenate
and magnesium salicylate, calcium phenate and magnesium phenate.
Overbased detergents are also preferred.
[0133] The detergent concentration in the lubricating oils of this
disclosure can range from about 0.5 to about 6.0 weight percent,
preferably about 0.6 to 5.0 weight percent, and more preferably
from about 0.8 weight percent to about 4.0 weight percent, based on
the total weight of the lubricating oil.
[0134] As used herein, the detergent concentrations are given on an
"as delivered" basis. Typically, the active detergent is delivered
with a process oil. The "as delivered" detergent typically contains
from about 20 weight percent to about 100 weight percent, or from
about 40 weight percent to about 60 weight percent, of active
detergent in the "as delivered" detergent product.
Other Antioxidants
[0135] Other antioxidants may be used in combination with the
monomeric, oligomeric and polymeric aminic antioxidants.
Antioxidants retard the oxidative degradation of base oils during
service. Such degradation may result in deposits on metal surfaces,
the presence of sludge, or a viscosity increase in the lubricant.
One skilled in the art knows a wide variety of oxidation inhibitors
that are useful in lubricating oil compositions. See, Klamann in
Lubricants and Related Products, op cite, and U.S. Pat. Nos.
4,798,684 and 5,084,197, for example.
[0136] Useful antioxidants include amine antioxidants, preferably
aromatic amine antioxidants. Other useful antioxidants include
phenolic antioxidants (e.g., hindered phenolic antioxidants).
Aromatic amine antioxidants may be used alone or in combination
with phenolic antioxidants. Typical examples of amine antioxidants
include: alkylated and non-alkylated aromatic amines such as
aromatic monoamines of the formula R.sup.8R.sup.9R.sup.10N where
R.sup.8 is an aliphatic, aromatic or substituted aromatic group,
R.sup.9 is an aromatic or a substituted aromatic group, and
R.sup.10 is H, alkyl, aryl or R.sup.11S(O)xR.sup.12 where R.sup.11
is an alkylene, alkenylene, or aralkylene group, R.sup.12 is a
higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is
0, 1 or 2. The aliphatic group R.sup.8 may contain from 1 to 20
carbon atoms, and preferably contains from 6 to 12 carbon atoms.
The aliphatic group is an aliphatic group. Preferably, both R.sup.8
and R.sup.9 are aromatic or substituted aromatic groups, and the
aromatic group may be a fused ring aromatic group such as naphthyl.
Aromatic groups R.sup.8 and R.sup.9 may be joined together with
other groups such as S.
[0137] Typical aromatic amine antioxidants have alkyl substituent
groups of at least 6 carbon atoms. Examples of aliphatic groups
include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the
aliphatic groups will not contain more than 14 carbon atoms. The
general types of amine antioxidants useful in the present
compositions include diphenylamines, phenyl naphthylamines,
phenothiazines, imidodibenzyls and diphenyl phenylene diamines.
Mixtures of two or more aromatic amines are also useful. Particular
examples of aromatic amine antioxidants useful in the present
disclosure include: p,p'-dioctyldiphenylamine;
t-octylphenyl-alpha-naphthylamine; phenyl-alpha-naphthylamine; and
p-octylphenyl-alpha-naphthylamine.
[0138] The arylamines antioxidants may be used individually or in
combination. Such additives may be used in an amount of 0.01 to 5
weight percent, preferably 0.01 to 1.5 weight percent, more
preferably zero to less than 1.5 weight percent, more preferably
zero to less than 1 weight percent.
[0139] The phenolic antioxidants may be used individually or in
combination. The phenolic antioxidants may provide potential
benefits in other performance aspects. Such additives may be used
in an amount of 0.01 to 1 weight percent, preferably 0.01 to 0.75
weight percent, more preferably zero to less than 0.5 weight
percent.
Viscosity Modifiers
[0140] Viscosity modifiers (also known as viscosity index improvers
(VI improvers), and viscosity improvers) can be included in the
lubricant compositions of this disclosure.
[0141] Viscosity modifiers provide lubricants with high and low
temperature operability. These additives impart shear stability at
elevated temperatures and acceptable viscosity at low
temperatures.
[0142] Suitable viscosity modifiers include high molecular weight
hydrocarbons, polyesters and viscosity modifier dispersants that
function as both a viscosity modifier and a dispersant. Typical
molecular weights of these polymers are between about 10,000 to
1,500,000, more typically about 20,000 to 1,200,000, and even more
typically between about 50,000 and 1,000,000.
[0143] Examples of suitable viscosity modifiers are linear or
star-shaped polymers and copolymers of methacrylate, butadiene,
olefins, or alkylated styrenes. Polyisobutylene is a commonly used
viscosity modifier. Another suitable viscosity modifier is
polymethacrylate (copolymers of various chain length alkyl
methacrylates, for example), some formulations of which also serve
as pour point depressants. Other suitable viscosity modifiers
include copolymers of ethylene and propylene, hydrogenated block
copolymers of styrene and isoprene, and polyacrylates (copolymers
of various chain length acrylates, for example). Specific examples
include styrene-isoprene or styrene-butadiene based polymers of
50,000 to 200,000 molecular weight.
[0144] Olefin copolymers are commercially available from Chevron
Oronite Company LLC under the trade designation "PARATONE.RTM."
(such as "PARATONE.RTM. 8921" and "PARATONE.RTM. 8941"); from Afton
Chemical Corporation under the trade designation "HiTEC.RTM." (such
as "HiTEC.RTM. 5850B"; and from The Lubrizol Corporation under the
trade designation "Lubrizol.RTM. 7067C". Hydrogenated polyisoprene
star polymers are commercially available from Infineum
International Limited, e.g., under the trade designation "SV200"
and "SV600". Hydrogenated diene-styrene block copolymers are
commercially available from Infineum International Limited, e.g.,
under the trade designation "SV 50".
[0145] The polymethacrylate or polyacrylate polymers can be linear
polymers which are available from Evnoik Industries under the trade
designation "Viscoplex.RTM." (e.g., Viscoplex 6-954) or star
polymers which are available from Lubrizol Corporation under the
trade designation Asteric.TM. (e.g., Lubrizol 87708 and Lubrizol
87725).
[0146] Illustrative vinyl aromatic-containing polymers useful in
this disclosure may be derived predominantly from vinyl aromatic
hydrocarbon monomer. Illustrative vinyl aromatic-containing
copolymers useful in this disclosure may be represented by the
following general formula:
A-B
wherein A is a polymeric block derived predominantly from vinyl
aromatic hydrocarbon monomer, and B is a polymeric block derived
predominantly from conjugated diene monomer.
[0147] In an embodiment of this disclosure, the viscosity modifiers
may be used in an amount of less than about 10 weight percent,
preferably less than about 7 weight percent, more preferably less
than about 4 weight percent, and in certain instances, may be used
at less than 2 weight percent, preferably less than about 1 weight
percent, and more preferably less than about 0.5 weight percent,
based on the total weight of the formulated oil or lubricating
engine oil. Viscosity modifiers are typically added as
concentrates, in large amounts of diluent oil.
[0148] As used herein, the viscosity modifier concentrations are
given on an "as delivered" basis. Typically, the active polymer is
delivered with a diluent oil. The "as delivered" viscosity modifier
typically contains from 20 weight percent to 75 weight percent of
an active polymer for polymethacrylate or polyacrylate polymers, or
from 8 weight percent to 20 weight percent of an active polymer for
olefin copolymers, hydrogenated polyisoprene star polymers, or
hydrogenated diene-styrene block copolymers, in the "as delivered"
polymer concentrate.
Pour Point Depressants (PPDs)
[0149] Conventional pour point depressants (also known as lube oil
flow improvers) may be added to the compositions of the present
disclosure if desired. These pour point depressant may be added to
lubricating compositions of the present disclosure to lower the
minimum temperature at which the fluid will flow or can be poured.
Examples of suitable pour point depressants include
polymethacrylates, polyacrylates, polyarylamides, condensation
products of haloparaffin waxes and aromatic compounds, vinyl
carboxylate polymers, and terpolymers of dialkylfumarates, vinyl
esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos.
1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746;
2,721,877; 2,721,878; and 3,250,715 describe useful pour point
depressants and/or the preparation thereof. Such additives may be
used in an amount of about 0.01 to 5 weight percent, preferably
about 0.01 to 1.5 weight percent.
Seal Compatibility Agents
[0150] Seal compatibility agents help to swell elastomeric seals by
causing a chemical reaction in the fluid or physical change in the
elastomer. Suitable seal compatibility agents for lubricating oils
include organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (butylbenzyl phthalate, for example), and polybutenyl
succinic anhydride. Such additives may be used in an amount of
about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight
percent.
Antifoam Agents
[0151] Anti-foam agents may advantageously be added to lubricant
compositions. These agents retard the formation of stable foams.
Silicones and organic polymers are typical anti-foam agents. For
example, polysiloxanes, such as silicon oil or polydimethyl
siloxane, provide antifoam properties. Anti-foam agents are
commercially available and may be used in conventional minor
amounts along with other additives such as demulsifiers; usually
the amount of these additives combined is less than 1 weight
percent and often less than 0.1 weight percent.
Inhibitors and Antirust Additives
[0152] Antirust additives (or corrosion inhibitors) are additives
that protect lubricated metal surfaces against chemical attack by
water or other contaminants. A wide variety of these are
commercially available.
[0153] One type of antirust additive is a polar compound that wets
the metal surface preferentially, protecting it with a film of oil.
Another type of antirust additive absorbs water by incorporating it
in a water-in-oil emulsion so that only the oil touches the metal
surface. Yet another type of antirust additive chemically adheres
to the metal to produce a non-reactive surface. Examples of
suitable additives include zinc dithiophosphates, metal phenolates,
basic metal sulfonates, fatty acids and amines. Such additives may
be used in an amount of about 0.01 to 5 weight percent, preferably
about 0.01 to 1.5 weight percent.
Friction Modifiers
[0154] A friction modifier is any material or materials that can
alter the coefficient of friction of a surface lubricated by any
lubricant or fluid containing such material(s). Friction modifiers,
also known as friction reducers, or lubricity agents or oiliness
agents, and other such agents that change the ability of base oils,
formulated lubricant compositions, or functional fluids, to modify
the coefficient of friction of a lubricated surface may be
effectively used in combination with the base oils or lubricant
compositions of the present disclosure if desired. Friction
modifiers that lower the coefficient of friction are particularly
advantageous in combination with the base oils and lube
compositions of this disclosure.
[0155] Illustrative friction modifiers may include, for example,
organometallic compounds or materials, or mixtures thereof.
Illustrative organometallic friction modifiers useful in the
lubricating engine oil formulations of this disclosure include, for
example, molybdenum amine, molybdenum diamine, an
organotungstenate, a molybdenum dithiocarbamate, molybdenum
dithiophosphates, molybdenum amine complexes, molybdenum
carboxylates, and the like, and mixtures thereof. Similar tungsten
based compounds may be preferable.
[0156] Other illustrative friction modifiers useful in the
lubricating engine oil formulations of this disclosure include, for
example, alkoxylated fatty acid esters, alkanolamides, polyol fatty
acid esters, borated glycerol fatty acid esters, fatty alcohol
ethers, and mixtures thereof.
[0157] Illustrative alkoxylated fatty acid esters include, for
example, polyoxyethylene stearate, fatty acid polyglycol ester, and
the like. These can include polyoxypropylene stearate,
polyoxybutylene stearate, polyoxyethylene isosterate,
polyoxypropylene isostearate, polyoxyethylene palmitate, and the
like.
[0158] Illustrative alkanolamides include, for example, lauric acid
diethylalkanolamide, palmic acid diethylalkanolamide, and the like.
These can include oleic acid diethyalkanolamide, stearic acid
diethylalkanolamide, oleic acid diethylalkanolamide,
polyethoxylated hydrocarbylamides, polypropoxylated
hydrocarbylamides, and the like.
[0159] Illustrative polyol fatty acid esters include, for example,
glycerol mono-oleate, saturated mono-, di-, and tri-glyceride
esters, glycerol mono-stearate, and the like. These can include
polyol esters, hydroxyl-containing polyol esters, and the like.
[0160] Illustrative borated glycerol fatty acid esters include, for
example, borated glycerol mono-oleate, borated saturated mono-,
di-, and tri-glyceride esters, borated glycerol mono-sterate, and
the like. In addition to glycerol polyols, these can include
trimethylolpropane, pentaerythritol, sorbitan, and the like. These
esters can be polyol monocarboxylate esters, polyol dicarboxylate
esters, and on occasion polyoltricarboxylate esters. Preferred can
be the glycerol mono-oleates, glycerol dioleates, glycerol
trioleates, glycerol monostearates, glycerol distearates, and
glycerol tristearates and the corresponding glycerol
monopalmitates, glycerol dipalmitates, and glycerol tripalmitates,
and the respective isostearates, linoleates, and the like. On
occasion the glycerol esters can be preferred as well as mixtures
containing any of these. Ethoxylated, propoxylated, butoxylated
fatty acid esters of polyols, especially using glycerol as
underlying polyol can be preferred.
[0161] Illustrative fatty alcohol ethers include, for example,
stearyl ether, myristyl ether, and the like. Alcohols, including
those that have carbon numbers from C.sub.3 to C.sub.50, can be
ethoxylated, propoxylated, or butoxylated to form the corresponding
fatty alkyl ethers. The underlying alcohol portion can preferably
be stearyl, myristyl, C.sub.11-C.sub.13 hydrocarbon, oleyl,
isosteryl, and the like.
[0162] The lubricating oils of this disclosure exhibit desired
properties, e.g., wear control, in the presence or absence of a
friction modifier.
[0163] Useful concentrations of friction modifiers may range from
0.01 weight percent to 5 weight percent, or about 0.1 weight
percent to about 2.5 weight percent, or about 0.1 weight percent to
about 1.5 weight percent, or about 0.1 weight percent to about 1
weight percent. Concentrations to of molybdenum-containing
materials are often described in terms of Mo metal
concentration.
[0164] Advantageous concentrations of Mo may range from 25 ppm to
700 ppm or more, and often with a preferred range of 50-200 ppm.
Friction modifiers of all types may be used alone or in mixtures
with the materials of this disclosure. Often mixtures of two or
more friction modifiers, or mixtures of friction modifier(s) with
alternate surface active material(s), are also desirable.
Antiwear Additives
[0165] A metal alkylthiophosphate and more particularly a metal
dialkyl dithio phosphate in which the metal constituent is zinc, or
zinc dialkyl dithio phosphate (ZDDP) can be a useful component of
the lubricating oils of this disclosure. ZDDP can be derived from
primary alcohols, secondary alcohols or mixtures thereof. ZDDP
compounds generally are of the formula
Zn[SP(S)(OR.sup.1)(OR.sup.2)].sub.2
where R.sup.1 and R.sup.2 are C.sub.1-C.sub.18 alkyl groups,
preferably C.sub.2-C.sub.12 alkyl groups. These alkyl groups may be
straight chain or branched. Alcohols used in the ZDDP can be
propanol, 2-propanol, butanol, secondary butanol, pentanols,
hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl
hexanol, alkylated phenols, and the like. Mixtures of secondary
alcohols or of primary and secondary alcohol can be preferred.
Alkyl aryl groups may also be used.
[0166] Preferable zinc dithiophosphates which are commercially
available include secondary zinc dithiophosphates such as those
available from for example, The Lubrizol Corporation under the
trade designations "LZ 677A", "LZ 1095" and "LZ 1371", from for
example Chevron Oronite under the trade designation "OLOA 262" and
from for example Afton Chemical under the trade designation "HITEC
7169".
[0167] The ZDDP is typically used in amounts of from about 0.3
weight percent to about 1.5 weight percent, preferably from about
0.4 weight percent to about 1.2 weight percent, more preferably
from about 0.5 weight percent to about 1.0 weight percent, and even
more preferably from about 0.6 weight percent to about 0.8 weight
percent, based on the total weight of the lubricating oil, although
more or less can often be used advantageously. Preferably, the ZDDP
is a secondary ZDDP and present in an amount of from about 0.6 to
1.0 weight percent of the total weight of the lubricating oil.
[0168] The types and quantities of performance additives used in
combination with the instant disclosure in lubricant compositions
are not limited by the examples shown herein as illustrations.
[0169] When lubricating oil compositions contain one or more of the
additives discussed above, the additive(s) are blended into the
composition in an amount sufficient for it to perform its intended
function. Typical amounts of such additives useful in the present
disclosure are shown in Table 1 below.
[0170] It is noted that many of the additives are shipped from the
additive manufacturer as a concentrate, containing one or more
additives together, with a certain amount of base oil diluents.
Accordingly, the weight amounts in the table below, as well as
other amounts mentioned herein, are directed to the amount of
active ingredient (that is the non-diluent portion of the
ingredient). The weight percent (wt %) indicated below is based on
the total weight of the lubricating oil composition.
TABLE-US-00002 TABLE 1 Typical Amounts of Other Lubricating Oil
Components Approximate Approximate Compound wt % (Useful) wt %
(Preferred) Antiwear 0.1-2 0.5-1 Dispersant 0.1-20 0.1-8 Detergent
0.1-20 0.1-8 Other Antioxidant 0.1-10 0.1-5 Friction Modifier
0.01-5 0.01-1.5 Pour Point Depressant 0.0-5 0.01-1.5 (PPD)
Anti-foam Agent 0.001-3 0.001-0.15 Viscosity Index Improver 0.0-8
0.1-6 (pure polymer basis) Inhibitor and Antirust 0.01-5
0.01-1.5
[0171] The foregoing additives are all commercially available
materials. These additives may be added independently but are
usually precombined in packages which can be obtained from
suppliers of lubricant oil additives. Additive packages with a
variety of ingredients, proportions and characteristics are
available and selection of the appropriate package will take the
requisite use of the ultimate composition into account.
[0172] The following non-limiting examples are provided to
illustrate the disclosure.
EXAMPLES
[0173] Engine oil candidates were formulated. All of the
ingredients used in the candidate formulated oils were commercially
available. The nomenclature of illustrative antioxidants used in
the candidate formulated oils include octylated/butylated
diphenylamine (Irganox.RTM. L57 from BASF Corporation) and
bis(nonylphenyl)amine (Irganox.RTM. L67 from BASF Corporation).
[0174] Irganox.RTM. L57 is a mixture of several different
substituted diphenyl amine antioxidants. The four most common
molecular weights, and the relative amounts, for the Irganox.RTM.
L57 constituents are as follows:
TABLE-US-00003 Molecular Weight % Content Monomer A 225.34 16
Monomer B 281.44 37 Monomer C 337.5 28 Monomer D 393.66 19
[0175] Oligomers from Irganox.RTM. L57 can be formed, for example,
self-oligomers like A+A, A+A+A, or C+C+C+C or mixed oligomers like
A+B, A+B+C, B+A+D+D in a myriad of combinations. When the monomers
of Irganox.RTM. L57 oligomerize, they can form dimers, trimers and
higher order oligomers in varying abundance which is in part
governed by the relative abundance of the monomers as well as the
relative reactivity of the monomer. The relative concentration of
higher order oligomers will decrease as the size of the oligomer
increases due to molecular diversity that is produced. As such, the
oligomers expected to be formed in the highest concentration will
be dimers, followed by trimers and so forth.
[0176] The candidates were fully formulated lubricants. In addition
to Irganox.RTM. L57, the formulations contained typical base stocks
combined with dispersants, detergents, antiwear additives, friction
modifiers, and the like.
[0177] Formulated oils including an inventive example (i.e.,
inventive Example 2 having 5 weight percent Irganox.RTM. L57) and a
comparative example (i.e., comparative Example 1 having 0.75 weight
percent Irganox.RTM. L57) were tested according to a Sequence IIIH
engine test until % viscosity increase exceeded 100%. The monomeric
aminic antioxidants were each added to an engine oil at the
indicated concentration. The Sequence IIIH Test (ASTM D8111) is a
fired-engine, dynamometer lubricant test for evaluating automotive
engine oils for certain high-temperature performance
characteristics, including oil thickening, varnish deposition and
oil consumption. The Sequence IIIH engine test results are shown
below.
TABLE-US-00004 Example 1 Example 2 Irganox L57 0.75 wt % 5 wt %
Sequence IIIH % Viscosity increase at 150 hours 118% 52% Average
Piston Varnish Merits 3.75 5.6 Average Piston Deposit Merits 8.66
9.79
[0178] The inventive Example 2 provided outstanding viscosity
performance while maintaining improved deposits performance. Lower
% viscosity increase is better. Higher "merits" is better.
[0179] Used oil samples from the Sequence IIIH engine testing were
analyzed by liquid chromatography mass spectrometry (LCMS) to
quantify the relative concentration of molecular ions of interest.
The data was then analyzed by the following equation:
[(oligomer ions at time point/total ions at time point)-(oligomer
ions at zero hours/total ions at zero hours)].times.1000=relative
amount of oligomers detected by LCMS
[0180] In this way, all data was normalized prior to the start of
the test. Values reported are the relative increase in the amount
of that oligomer. Values less than 1 can be considered noise in the
system, while values greater than 1 represent a real increase in
the amount of an oligomer.
[0181] Ion counts for oligomers of Irganox.RTM. L57 in comparative
Example 1 formulated oil analyzed by LCMS are shown in FIG. 1.
[0182] Ion counts for oligomers of Irganox.RTM. L57 in inventive
Example 2 formulated oil analyzed by LCMS are shown in FIG. 2.
[0183] In an embodiment, a preformed oligomeric or polymeric aminic
antioxidant can be co-formulated with a monomeric aminic
antioxidant. The presence of additional monomeric aminic
antioxidant starting material allows for the oligomeric or
polymeric antioxidant to form even larger oligomers and polymers
and regenerate itself throughout the oil drain interval.
[0184] In particular, in addition to formulated oils containing
only monomeric aminic antioxidants, there can also be oils that are
formulated with an oligomeric aminic antioxidant (such as MCP 2568,
Nycoperf.RTM. A0337, or Vanlube.RTM. 9317) in addition to a
monomeric aminic antioxidant (such as Irganox.RTM. L57,
Irganox.RTM. L67, or Irganox.RTM. L06). In this embodiment, the
monomeric aminic antioxidant can further react with the preexisting
oligomeric aminic antioxidants to form various combinations of even
higher order oligomers. This function is self-healing as the newly
attached monomers replace other portions of the preexisting
oligomer that have degraded during the lifetime of the formulated
oil. This additional oligomerization can also improve the
antioxidancy of the preexisting oligomers, as some higher order
oligomers are more potent antioxidants than lower order
oligomers.
[0185] In another embodiment, simplified formulations containing
only monomeric aminic antioxidant and base stock, generate in situ
oligomeric and polymeric aminic antioxidants in lubricating oil
formulations.
[0186] In yet another embodiment, some consumers have a particular
preference for oils that are not dark in color. The color of a
formulated oil can be measured using various methods, including
ASTM D1500. In this embodiment, it is sometimes preferable to have
a formulated oil with a color less than 6 according to ASTM D1500.
Current available oligomeric aminic antioxidants often suffer from
the problem of being very dark in nature. When used in a formulated
oil at an appropriate treat rate, these materials can result in a
final formulation color that is unacceptable to the consumer. One
particular advantage of this disclosure is that these formulations
are not dark in nature because monomeric aminic antioxidants tend
to be much lighter in color according to ASTM D1500.
[0187] The lubricating oils of this disclosure can also be test in
accordance with the General Motors Oxidation and Deposit Test
(GMOD) in accordance with GMW17043, 2.sup.nd Edition, May 2016. The
GMOD test procedure covers engine tests for evaluating automotive
engine oils for certain high temperature performance
characteristics, including oil thickening, and piston deposits.
Additionally, secondary requirements that can be conducted include
mini rotary viscometer measurements, cold cranking simulator
measurements, and phosphorus retention measurements.
[0188] It has been found that, with in situ generated oligomeric
and polymeric aminic antioxidants in lubricating oil formulations,
viscosity control and deposit control are improved in the finished
formulations designed for engine oil applications.
ADDITIONAL EMBODIMENTS
Embodiment 1
[0189] A method for controlling formation and dissipation of at
least one oligomeric or polymeric aminic antioxidant in a
lubricating oil, during operation of an engine or other mechanical
component lubricated with the lubricating oil by using as the
lubricating oil a formulated oil, said formulated oil having a
composition comprising a lubricating oil base stock as a major
component; and at least one oligomeric or polymeric aminic
antioxidant, as a minor component; wherein the at least one
oligomeric or polymeric aminic antioxidant is formed over time in
situ from at least one monomeric aminic antioxidant during
operation of the engine or other mechanical component; wherein the
at least one oligomeric or polymeric aminic antioxidant is
dissipated over time in the lubricating oil during operation of the
engine or other mechanical component; wherein the lubricating oil
base stock is present in an amount from about 1 to about 95 weight
percent, based on the total weight of the lubricating oil; and
wherein the at least one monomeric aminic antioxidant is present in
an amount from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil.
Embodiment 2
[0190] The method of claim 1 wherein, in measurements of the
lubricating oil by a Sequence IIIH engine test in accordance with
ASTM D8111-17, viscosity control and deposit control are improved
using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 3
[0191] The method of claim 1 wherein the at least one monomeric
aminic antioxidant comprises at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures
thereof.
Embodiment 4
[0192] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 5
[0193] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant comprises:
##STR00013##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 6
[0194] The method of claim 1 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00014##
[0195] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00015##
Embodiment 7
[0196] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of
##STR00016##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 8
[0197] The method of claim 7 wherein the at least one oligomeric or
polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or
mixtures thereof.
Embodiment 9
[0198] The method of claim 7 wherein the at least one oligomeric or
polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00017##
[0199] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00018##
Embodiment 10
[0200] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of:
##STR00019##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, p, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
Embodiment 11
[0201] The method of claim 1 wherein the lubricating oil base stock
is present in an amount from about 1 to about 80 weight percent,
based on the total weight of the lubricating oil.
Embodiment 12
[0202] The method of claim 1 wherein the at least one monomeric
aminic antioxidant is present in an amount from about 4 to about 8
weight percent, based on the total weight of the lubricating
oil.
Embodiment 13
[0203] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is present in an amount from about 0.1
to about 5 weight percent, based on the total weight of the
lubricating oil.
Embodiment 14
[0204] The method of claim 1 wherein the formulated oil further
comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
Embodiment 15
[0205] The method of claim 14 wherein the other antioxidant
comprises at least one aromatic amine antioxidant, at least one
phenolic antioxidant, or mixtures thereof.
Embodiment 16
[0206] The method of claim 1 wherein the at least one oligomeric or
polymeric aminic antioxidant is formed over time in situ during a
Sequence IIIH engine test in accordance with ASTM D8111-17, or a
General Motors Oxidation and Deposit Test (GMOD) in accordance with
GMW17043, 2.sup.nd Edition, May 2016.
Embodiment 17
[0207] The method of claim 1 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO), a commercial vehicle engine
oil (CVEO), or a lubricating oil that is subjected to heat and
oxidative conditions.
Embodiment 18
[0208] A method for controlling formation and dissipation of at
least one oligomeric or polymeric aminic antioxidant in a
lubricating oil, during operation of an engine or other mechanical
component lubricated with the lubricating oil by using as the
lubricating oil a formulated oil, said formulated oil having a
composition comprising a lubricating oil base stock as a major
component; and at least one monomeric aminic antioxidant, as a
minor component; wherein at least one oligomeric or polymeric
aminic antioxidant is formed over time in situ from the at least
one monomeric aminic antioxidant during operation of the engine or
other mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component; wherein the lubricating oil base stock is present in an
amount from about 1 to about 95 weight percent, based on the total
weight of the lubricating oil; and wherein the at least one
monomeric aminic antioxidant is present in an amount from greater
than about 2 to about 10 weight percent, based on the total weight
of the lubricating oil.
Embodiment 19
[0209] The method of claim 18 wherein, in measurements of the
lubricating oil by a Sequence IIIH engine test in accordance with
ASTM D8111-17, viscosity control and deposit control are improved
using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 20
[0210] The method of claim 18 wherein the at least one monomeric
aminic antioxidant comprises at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures
thereof.
Embodiment 21
[0211] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 22
[0212] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant comprises:
##STR00020##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 23
[0213] The method of claim 18 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00021##
[0214] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00022##
Embodiment 24
[0215] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of
##STR00023##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 25
[0216] The method of claim 24 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or
mixtures thereof.
Embodiment 26
[0217] The method of claim 24 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00024##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00025##
Embodiment 27
[0218] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of:
##STR00026##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, p, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
Embodiment 28
[0219] The method of claim 18 wherein the lubricating oil base
stock is present in an amount from about 1 to about 80 weight
percent, based on the total weight of the lubricating oil.
Embodiment 29
[0220] The method of claim 18 wherein the at least one monomeric
aminic antioxidant is present in an amount from about 4 to about 8
weight percent, based on the total weight of the lubricating
oil.
Embodiment 30
[0221] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant is present in an amount from about
0.1 to about 5 weight percent, based on the total weight of the
lubricating oil.
Embodiment 31
[0222] The method of claim 18 wherein the formulated oil further
comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
Embodiment 32
[0223] The method of claim 31 wherein the other antioxidant
comprises at least one aromatic amine antioxidant, at least one
phenolic antioxidant, or mixtures thereof.
Embodiment 33
[0224] The method of claim 18 wherein the at least one oligomeric
or polymeric aminic antioxidant is formed over time in situ during
a Sequence IIIH engine test in accordance with ASTM D8111-17, or a
General Motors Oxidation and Deposit Test (GMOD) in accordance with
GMW17043, 2.sup.nd Edition, May 2016.
Embodiment 34
[0225] The method of claim 18 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO), a commercial vehicle engine
oil (CVEO), or a lubricating oil that is subjected to heat and
oxidative conditions.
Embodiment 35
[0226] A method for controlling formation and dissipation of at
least one oligomeric or polymeric aminic antioxidant in a
lubricating oil, during operation of an engine or other mechanical
component lubricated with the lubricating oil by using as the
lubricating oil a formulated oil, said formulated oil having a
composition comprising a lubricating oil base stock as a major
component; and at least one oligomeric or polymeric aminic
antioxidant and at least one monomeric aminic antioxidant, as minor
components; wherein the at least one oligomeric or polymeric aminic
antioxidant and the at least one monomeric aminic antioxidant react
to form over time in situ at least one oligomeric or polymeric
aminic antioxidant reaction product during operation of the engine
or other mechanical component; wherein the at least one oligomeric
or polymeric aminic antioxidant reaction product is dissipated over
time in the lubricating oil during operation of the engine or other
mechanical component; wherein the lubricating oil base stock is
present in an amount from about 1 to about 95 weight percent, based
on the total weight of the lubricating oil; wherein the at least
one oligomeric or polymeric aminic antioxidant is present in an
amount from greater than about 0.1 to about 10 weight percent,
based on the total weight of the lubricating oil; and wherein the
at least one monomeric aminic antioxidant is present in an amount
from greater than about 2 to about 10 weight percent, based on the
total weight of the lubricating oil.
Embodiment 36
[0227] The method of claim 35 wherein, in measurements of the
lubricating oil by a Sequence IIIH engine test in accordance with
ASTM D8111-17, viscosity control and deposit control are improved
using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 37
[0228] The method of claim 35 wherein the at least one monomeric
aminic antioxidant comprises at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures
thereof.
Embodiment 38
[0229] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 39
[0230] The method of claim 35 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00027##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 40
[0231] The method of claim 35 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00028##
[0232] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00029##
Embodiment 41
[0233] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of
##STR00030##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 42
[0234] The method of claim 41 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or
mixtures thereof.
Embodiment 43
[0235] The method of claim 41 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00031##
[0236] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00032##
Embodiment 44
[0237] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of:
##STR00033##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, p, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
Embodiment 45
[0238] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant reaction product is the
oligomerization or polymerization reaction product of:
##STR00034##
[0239] wherein (A) and (B) each range from zero to 10, provided
(A)+(B) is at least 2; R.sup.2 is a styrene or C1 to C30 alkyl,
R.sup.3 is a styrene or C1 to C30 alkyl, q and y individually range
from 0 to up to the valence of the aryl group to which the
respective R groups are attached; with at least one monomeric
aminic antioxidant comprising:
##STR00035##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00036##
Embodiment 46
[0240] The method of claim 35 wherein the lubricating oil base
stock is present in an amount from about 1 to about 80 weight
percent, based on the total weight of the lubricating oil.
Embodiment 47
[0241] The method of claim 35 wherein the at least one monomeric
aminic antioxidant is present in an amount from about 4 to about 8
weight percent, based on the total weight of the lubricating
oil.
Embodiment 48
[0242] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant is present in an amount from about
1 to about 8 weight percent, based on the total weight of the
lubricating oil.
Embodiment 49
[0243] The method of claim 35 wherein the formulated oil further
comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
Embodiment 50
[0244] The method of claim 49 wherein the other antioxidant
comprises at least one aromatic amine antioxidant, at least one
phenolic antioxidant, or mixtures thereof.
Embodiment 51
[0245] The method of claim 35 wherein the at least one oligomeric
or polymeric aminic antioxidant is formed over time in situ during
a Sequence IIIH engine test in accordance with ASTM D8111-17, or a
General Motors Oxidation and Deposit Test (GMOD) in accordance with
GMW17043, 2.sup.nd Edition, May 2016.
Embodiment 52
[0246] The method of claim 35 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO), a commercial vehicle engine
oil (CVEO), or a lubricating oil that is subjected to heat and
oxidative conditions.
Embodiment 53
[0247] A method for regenerating at least one oligomeric or
polymeric aminic antioxidant in a lubricating oil, during operation
of an engine or other mechanical component lubricated with the
lubricating oil by using as the lubricating oil a formulated oil,
said formulated oil having a composition comprising a lubricating
oil base stock as a major component; and at least one oligomeric or
polymeric aminic antioxidant and at least one monomeric aminic
antioxidant, as minor components; wherein the at least one
oligomeric or polymeric aminic antioxidant dissipates over time in
the lubricating oil during operation of the engine or other
mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant and the at least one monomeric aminic
antioxidant react to form over time in situ at least one
regenerated oligomeric or polymeric aminic antioxidant during
operation of the engine or other mechanical component; wherein the
lubricating oil base stock is present in an amount from about 1 to
about 95 weight percent, based on the total weight of the
lubricating oil; wherein the at least one oligomeric or polymeric
aminic antioxidant is present in an amount from greater than about
0.1 to about 10 weight percent, based on the total weight of the
lubricating oil; and wherein the at least one monomeric aminic
antioxidant is present in an amount from greater than about 2 to
about 10 weight percent, based on the total weight of the
lubricating oil.
Embodiment 54
[0248] The method of claim 53 wherein, in measurements of the
lubricating oil by a Sequence IIIH engine test in accordance with
ASTM D8111-17, viscosity control and deposit control are improved
using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 55
[0249] The method of claim 53 wherein the at least one monomeric
aminic antioxidant comprises at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures
thereof.
Embodiment 56
[0250] The method of claim 53 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 57
[0251] The method of claim 53 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00037##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 58
[0252] The method of claim 53 wherein the at least one monomeric
aminic antioxidant comprises:
##STR00038##
[0253] wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00039##
Embodiment 59
[0254] The method of claim 53 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product of
##STR00040##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 60
[0255] The method of claim 59 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or
mixtures thereof.
Embodiment 61
[0256] The method of claim 59 wherein the at least one oligomeric
or polymeric aminic antioxidant is the oligomerization or
polymerization reaction product formed by any combination of:
##STR00041##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00042##
Embodiment 62
[0257] The method of claim 53 wherein the at least one oligomeric
or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of:
##STR00043##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, p, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
Embodiment 63
[0258] The method of claim 53 wherein the at least one regenerated
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product of:
##STR00044##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached; with at least one monomeric aminic antioxidant
comprising:
##STR00045##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00046##
Embodiment 64
[0259] The method of claim 53 wherein the lubricating oil base
stock is present in an amount from about 1 to about 80 weight
percent, based on the total weight of the lubricating oil.
Embodiment 65
[0260] The method of claim 53 wherein the at least one monomeric
aminic antioxidant is present in an amount from about 4 to about 8
weight percent, based on the total weight of the lubricating
oil.
Embodiment 66
[0261] The method of claim 53 wherein the at least one oligomeric
or polymeric aminic antioxidant is present in an amount from about
1 to about 8 weight percent, based on the total weight of the
lubricating oil.
Embodiment 67
[0262] The method of claim 53 wherein the formulated oil further
comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
Embodiment 68
[0263] The method of claim 67 wherein the other antioxidant
comprises at least one aromatic amine antioxidant, at least one
phenolic antioxidant, or mixtures thereof.
Embodiment 69
[0264] The method of claim 53 wherein the at least one oligomeric
or polymeric aminic antioxidant is formed over time in situ during
a Sequence IIIH engine test in accordance with ASTM D8111-17, or a
General Motors Oxidation and Deposit Test (GMOD) in accordance with
GMW17043, 2.sup.nd Edition, May 2016.
Embodiment 70
[0265] The method of claim 53 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO), a commercial vehicle engine
oil (CVEO), or a lubricating oil that is subjected to heat and
oxidative conditions.
Embodiment 71
[0266] A lubricating oil having a composition comprising a
lubricating oil base stock as a major component, and at least one
oligomeric or polymeric aminic antioxidant, as a minor component;
wherein, in an engine or other mechanical component lubricated with
the lubricating oil, the at least one oligomeric or polymeric
aminic antioxidant is formed over time in situ from at least one
monomeric aminic antioxidant during operation of the engine or
other mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component; wherein the lubricating oil base stock is present in an
amount from about 1 to about 95 weight percent, based on the total
weight of the lubricating oil; and wherein the at least one
monomeric aminic antioxidant is present in an amount from greater
than about 2 to about 10 weight percent, based on the total weight
of the lubricating oil.
Embodiment 72
[0267] The lubricating oil of claim 71 wherein, in measurements of
the lubricating oil by a Sequence IIIH engine test in accordance
with ASTM D8111-17, viscosity control and deposit control are
improved using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 73
[0268] The lubricating oil of claim 71 wherein the at least one
monomeric aminic antioxidant comprises at least one unsubstituted
or hydrocarbyl-substituted diphenyl amine, at least one
unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or
mixtures thereof.
Embodiment 74
[0269] The lubricating oil of claim 71 wherein the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 75
[0270] The lubricating oil of claim 71 wherein the at least one
monomeric aminic antioxidant comprises:
##STR00047##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or
[0271] C1 to C30 alkyl, R.sup.3 is a styrene or C1 to C30 alkyl, q
and y individually range from 0 to up to the valence of the aryl
group to which the respective R groups are attached.
Embodiment 76
[0272] The lubricating oil of claim 71 wherein the at least one
monomeric aminic antioxidant comprises:
##STR00048##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00049##
Embodiment 77
[0273] The lubricating oil of claim 71 wherein the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product of
##STR00050##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at least 2; R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, q and y individually range from 0 to up
to the valence of the aryl group to which the respective R groups
are attached.
Embodiment 78
[0274] The lubricating oil of claim 77 wherein the at least one
oligomeric or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product comprising: (A)(A), (A)(B), (B)(B),
(A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A),
(A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B),
(B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A
Embodiment 79
[0275] The lubricating oil of claim 77 wherein the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product formed by any combination
of:
##STR00051##
wherein R is H, C.sub.4H.sub.9, C.sub.8H.sub.17, or
C.sub.9H.sub.19; and/or
##STR00052##
Embodiment 80
[0276] The lubricating oil of claim 71 wherein the at least one
oligomeric or polymeric aminic antioxidant is an oligomerization or
polymerization reaction product selected from the group consisting
of:
##STR00053##
wherein R.sup.2 is a styrene or C1 to C30 alkyl, R.sup.3 is a
styrene or C1 to C30 alkyl, R.sup.4 is a styrene or C1 to C30
alkyl, p, q and y individually range from 0 to up to the valence of
the aryl group to which the respective R groups are attached.
Embodiment 81
[0277] The lubricating oil of claim 71 wherein the lubricating oil
base stock is present in an amount from about 1 to about 80 weight
percent, based on the total weight of the to lubricating oil.
Embodiment 82
[0278] The lubricating oil of claim 71 wherein the at least one
monomeric aminic antioxidant is present in an amount from about 4
to about 8 weight percent, based on the total weight of the
lubricating oil.
Embodiment 83
[0279] The lubricating oil of claim 71 wherein the at least one
oligomeric or polymeric aminic antioxidant is present in an amount
from about 1 to about 8 weight percent, based on the total weight
of the lubricating oil.
Embodiment 84
[0280] The lubricating oil of claim 71 wherein the formulated oil
further comprises one or more of a viscosity modifier, dispersant,
detergent, other antioxidant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, and anti-rust additive.
Embodiment 85
[0281] The lubricating oil of claim 84 wherein the other
antioxidant comprises at least one aromatic amine antioxidant, at
least one phenolic antioxidant, or mixtures thereof.
Embodiment 86
[0282] The lubricating oil of claim 71 wherein the at least one
oligomeric or polymeric aminic antioxidant is formed over time in
situ during a Sequence IIIH engine test in accordance with ASTM
D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in
accordance with GMW17043, 2.sup.nd Edition, May 2016.
Embodiment 87
[0283] The lubricating oil of claim 71 which is a passenger vehicle
engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a
lubricating oil that is subjected to heat and oxidative
conditions.
Embodiment 88
[0284] A lubricating oil having a composition comprising a
lubricating oil base stock as a major component, and at least one
monomeric aminic antioxidant, as a minor component; wherein, in an
engine or other mechanical component lubricated with the
lubricating oil, at least one oligomeric or polymeric aminic
antioxidant is formed over time in situ from the at least one
monomeric aminic antioxidant during operation of the engine or
other mechanical component; wherein the at least one oligomeric or
polymeric aminic antioxidant is dissipated over time in the
lubricating oil during operation of the engine or other mechanical
component; wherein the lubricating oil base stock is present in an
amount from about 1 to about 95 weight percent, based on the total
weight of the lubricating oil; and wherein the at least one
monomeric aminic antioxidant is present in an amount from greater
than about 2 to about 10 weight percent, based on the total weight
of the lubricating oil.
Embodiment 89
[0285] The lubricating oil of claim 88 wherein, in measurements of
the lubricating oil by a Sequence IIIH engine test in accordance
with ASTM D8111-17, viscosity control and deposit control are
improved using a concentration of the at least one monomeric aminic
antioxidant from greater than about 2 to about 10 weight percent,
based on the total weight of the lubricating oil, as compared to
viscosity control and deposit control achieved using a lower
concentration of the at least one monomeric aminic antioxidant.
Embodiment 90
[0286] The lubricating oil of claim 88 wherein the at least one
monomeric aminic antioxidant comprises at least one unsubstituted
or hydrocarbyl-substituted diphenyl amine, at least one
unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or
mixtures thereof.
Embodiment 91
[0287] The lubricating oil of claim 88 wherein the at least one
oligomeric or polymeric aminic antioxidant is the oligomerization
or polymerization reaction product of at least one unsubstituted or
hydrocarbyl-substituted diphenyl amine, at least one unsubstituted
or hydrocarbyl-substituted phenyl naphthyl amine, or both at least
one unsubstituted or hydrocarbyl-substituted diphenylamine and at
least one unsubstituted or hydrocarbyl-substituted phenyl
naphthylamine.
Embodiment 92
[0288] The lubricating oil of claim 88 wherein the at least one
monomeric to aminic antioxidant comprises:
##STR00054##
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is
at le
References