U.S. patent application number 14/505157 was filed with the patent office on 2015-04-09 for low viscosity/low volatility lubricant oil compositions comprising alkylated naphthalenes.
The applicant listed for this patent is King Industries, Inc. Invention is credited to Farouk Abi-Karam, Richard A. Abramshe, Angela C. Bylo, Ramanathan Ravichandran.
Application Number | 20150099678 14/505157 |
Document ID | / |
Family ID | 52777425 |
Filed Date | 2015-04-09 |
United States Patent
Application |
20150099678 |
Kind Code |
A1 |
Abi-Karam; Farouk ; et
al. |
April 9, 2015 |
Low Viscosity/Low Volatility Lubricant Oil Compositions Comprising
Alkylated Naphthalenes
Abstract
Provided herein is are low viscosity, low volatility lubricant
oil compositions comprising a first base oil component comprising,
for example, alkylated naphthalenes, and a second base oil
component wherein the composition has a kinematic viscosity at
100.degree. C. of 7.6 cSt or less, a Noack volatility at
250.degree. C. of less than 10%, and a viscosity index of at least
90 for use as internal combustion engine oils, such as compression-
and spark-ignition engine oils.
Inventors: |
Abi-Karam; Farouk; (Wilton,
CT) ; Abramshe; Richard A.; (Highland, NY) ;
Ravichandran; Ramanathan; (Suffern, NY) ; Bylo;
Angela C.; (Seymour, CT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
King Industries, Inc, |
Norwalk |
CT |
US |
|
|
Family ID: |
52777425 |
Appl. No.: |
14/505157 |
Filed: |
October 2, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61886410 |
Oct 3, 2013 |
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Current U.S.
Class: |
508/591 |
Current CPC
Class: |
C10M 111/06 20130101;
C10N 2030/02 20130101; C10N 2030/74 20200501; C10N 2020/02
20130101; C10M 2205/223 20130101; C10N 2040/25 20130101; C10M
2207/2805 20130101; C10M 2203/1025 20130101; C10M 2205/0285
20130101; C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M
2203/1025 20130101; C10N 2020/02 20130101 |
Class at
Publication: |
508/591 |
International
Class: |
C10M 111/04 20060101
C10M111/04 |
Claims
1. A lubricant oil composition comprising (a) a first base oil
component in the amount of 1 weight % to 50 weight % based on the
total weight of the oil composition, wherein the first base oil
component comprises a compound of Formula (I) ##STR00006## wherein
R is (C.sub.18-C.sub.40)alkyl, (C.sub.5-C.sub.40)cycloalkyl,
(C.sub.5-C.sub.40)aryl, (C.sub.7-C.sub.9)aralkyl; wherein the
aralkyl is optionally substituted with (C.sub.1-C.sub.36)alkyl, or
(C.sub.6-C.sub.40)alkenyl; and (b) a second base oil component in
the amount of 0.1 weight % to 80 weight % based on the total weight
of the oil composition, wherein the second base oil component
comprises one or more of a polyalphaolefin (PAO) base stock, Group
II base stock, Group III base stock, Group V base stock, GTL base
stock, alkylated benzene base stock, and ester base stock; wherein
the composition has a kinematic viscosity at 100.degree. C. of 7.6
cSt or less, a Noack volatility at 250.degree. C. of less than 10%,
and a viscosity index of at least 90.
2. The lubricant oil composition of claim 1, wherein the second
base oil component comprises a polyalphaolefin (PAO) base
stock.
3. The lubricant oil composition of claim 1, wherein the second
base oil component comprises Group II base stock.
4. The lubricant oil composition of claim 1, wherein the second
base oil component comprises Group III base stock.
5. The lubricant oil composition of claim 1, wherein the second
base oil component comprises Group V base stock.
6. The lubricant oil composition of claim 1, wherein the second
base oil component comprises GTL base stock.
7. The lubricant oil composition of claim 1, wherein the second
base oil component comprises alkylated benzene base stock.
8. The lubricant oil composition of claim 1, wherein the second
base oil component comprises ester base stock.
9. The lubricant oil composition of any one of claims 1-8, wherein
first base oil component has a kinematic viscosity at 100.degree.
C. of equal or less than 7.0 cSt, a Noack volatility at 250.degree.
C. of less than 8%, and a viscosity index equal or higher than
80.
10. The lubricant oil composition of any one of claims 1-9, wherein
the composition has a kinematic viscosity at 100.degree. C. of 6.0
cSt or less.
11. The lubricant oil composition of any one of claim 1, 9, or 10,
wherein the kinematic viscosity is determined by ASTM D445.
12. The lubricant oil composition of any one of claim 1, 9, or 10,
wherein the Noack volatility is determined by ASTM D5800.
13. The lubricant oil composition of any one of claim 1, 9, or 10,
wherein the Noack volatility is determined by ASTM D2270.
14. The lubricant oil composition of any one of claims 1-13,
wherein R is (C.sub.18-C.sub.32)alkyl.
15. The lubricant oil composition of any one of claims 1-14,
wherein R is (C.sub.20-C.sub.24)alkyl.
16. The lubricant oil composition of any one of claims 1-14,
wherein R is C.sub.18 alkyl.
17. The lubricant oil composition of any one of claims 1-15,
wherein R is C.sub.20 alkyl.
18. The lubricant oil composition of any one of claims 1-14,
wherein R is C.sub.32 alkyl.
19. The lubricant oil composition of any one of claims 1-10,
wherein the first base oil component comprises a mixture of two or
more compounds of Formula (I), wherein at least one compound is a
compound of Formula (I), wherein R is a C.sub.20 alkyl and at least
one compound is a compound of Formula (I), wherein R is a C.sub.24
alkyl.
20. The lubricant oil composition of any one of claims 1-10,
wherein the first base oil component comprises a mixture of two or
more compounds of Formula (I), wherein at least one compound is a
compound of Formula (I), wherein R is a C.sub.18 alkyl and at least
one compound is a compound of Formula (I), wherein R is a
(C.sub.20-C.sub.24)alkyl.
21. The lubricant oil composition of any one of claims 1-14,
wherein R is (C.sub.18-C.sub.32) Guerbet alkyl.
22. The lubricant oil composition of any one of claims 1-14 and 21,
wherein R is C.sub.18 Guerbet alkyl.
23. The lubricant oil composition of any one of claims 1-14 and 21,
wherein R is C.sub.20 Guerbet alkyl.
24. The lubricant oil composition of any one of claims 1-14 and 21,
wherein R is C.sub.24 Guerbet alkyl.
25. The lubricant oil composition of any one of claims 1-14 and 21,
wherein R is C.sub.28 Guerbet alkyl.
26. The lubricant oil composition of any one of claims 1-14 and 21,
wherein R is C.sub.32 Guerbet alkyl.
27. The lubricant oil composition of any one of claims 1-26,
wherein the lubricant oil composition further comprises one or more
additives, wherein each additive independently is a detergent, a
dispersant, an antioxidant, a pour point depressant, a VI improver,
an anti-wear agent, an extreme pressure additive, a friction
modifier, a demulsifier, an antifoamant, a corrosion inhibitor, a
seal swell control additive, or a metal deactivator.
28. The lubricant oil composition of any one of claims 1-27,
wherein the lubricant oil composition further comprises one or more
additives, wherein each additive independently is a detergent, a
dispersants, an antioxidant, an anti-wear agent, or a VI
improver.
29. The lubricant oil composition of any one of claims 1-28,
wherein the lubricant oil composition has one or more of the
following properties selected from the group consisting of
oxidation resistance, swell characteristics, deposit performance,
reserve alkalinity, rust preventing quality, and levels of
ash-forming compound, improved as compared to an oil composition
comprising the second base oil component, but not comprising the
first base oil component.
30. An internal combustion engine oil comprising a lubricant oil
composition of any one of claims 1-28.
31. A compression-ignition engine oil comprising a lubricant oil
composition of any one of claims 1-28.
32. A spark-ignition engine oil comprising a lubricant oil
composition of any one of claims 1-28.
33. A method of improving fuel efficiency in an internal combustion
engine by lubricating said engine with a lubricant oil composition
of any one of claims 1-25, wherein the fuel efficiency is improved
as compared to fuel efficiency achieved by lubricating said engine
with an oil composition comprising the second base oil component,
but not comprising the first base oil component.
34. A method of improving oxidation resistance, swell
characteristics, deposit performance, reserve alkalinity, rust
preventing quality, or levels of ash-forming compounds of a
lubricating oil composition by mixing a first base oil component of
any one of claim 1, 9, or 14-26 with a second base oil component of
any one of claims 1-8 and optionally one or more additives, wherein
said oxidation resistance, swell characteristics, deposit
performance, reserve alkalinity, rust preventing quality, or levels
of ash-forming compound of a lubricating oil composition are
improved as compared to an oil composition comprising the second
base oil component, but not comprising the first base oil
component.
Description
[0001] This application claims the benefit of U.S. provisional
application No. 61/886,410, filed Oct. 3, 2013, which is herewith
incorporated by reference in its entirety.
1 FIELD
[0002] Provided herein are low viscosity, low volatility lubricant
oil compositions comprising a first base oil component comprising,
for example, alkylated naphthalenes, and a second base oil
component wherein the composition has a kinematic viscosity at
100.degree. C. of about 7.6 cSt or less, a Noack volatility at
250.degree. C. of less than about 10%, and a viscosity index of at
least about 90 for use as internal combustion engine oils, such as
compression- or spark-ignition engine oils.
2 BACKGROUND
[0003] Lubricating oils are critical to the operation of the
machinery of the world today. Synthetic lubricants in the engine
crankcase, rear axle, and transmission can improve fuel economy by
about 3 percent, saving nearly 485 gallons of fuel and eliminating
5 metric tons of greenhouse gas emissions for a typical combination
truck each year. Lubricants reduce friction and wear of critical
vehicle systems including the engine, transmission and drive train.
Without lubricants, the moving parts inside these systems would
grind together, causing heat, stress and wear. Recent changes in
legislation and new emission standards, for example PC-11 for
heavy-duty diesel engines and GF-6 for passenger automobiles, have
increased pressure on vehicle manufacturers to improve fuel
efficiency and reduce emissions.
[0004] Within an engine there are two types of friction that impact
fuel economy. One that is related to the thickness of the oil
classified as viscous friction which leads to energy losses due to
the pumping of the viscous oil through the engine, especially
during cold engine start up and stop and go driving. The other,
contact friction resulting from contact between moving metal
surfaces leads to engine wear and reduced fuel economy.
[0005] Conventional mineral oil lubricants due to their higher
viscosity are unable to effectively slip between and lubricate the
moving parts of these systems, particularly in newer truck
components that are designed with close tolerances and tight fits.
Conventional higher viscosity lubricants may also be making it
harder for pumps, gears and shafts to move. These effects create
energy losses and friction losses, and waste fuel.
[0006] Low-viscosity lubricants are less resistant to flow than
lubricants presently known, a property that helps reduce friction
and lowering the energy wasted pumping the oil through the
engine.
[0007] Attempts have been made to use conventional low viscosity
polyalphaolefin ("PAO") base stocks to achieve low viscosity engine
oil formulations. The volatility requirements for engine oils,
however, limit the amount of low viscosity conventional PAO that
can be used and the extent to which the viscosity of the engine oil
formulation can be reduced.
[0008] Therefore, new low viscosity/low volatility lubricant oil
compositions to further improve fuel efficiency are desirable.
3 SUMMARY
[0009] Provided herein is a lubricant oil composition comprising
[0010] (a) a first base oil component in the amount of about 1
weight % to about 50 weight % based on the total weight of the oil
composition, wherein the first base oil component comprises a
compound of Formula I
[0010] ##STR00001## wherein R is (C.sub.18-C.sub.40)alkyl,
(C.sub.5-C.sub.40)cycloalkyl, (C.sub.5-C.sub.40)aryl,
(C.sub.7-C.sub.9)aralkyl; wherein the aralkyl is optionally
substituted with (C.sub.1-C.sub.36)alkyl, or
(C.sub.6-C.sub.40)alkenyl; and [0011] (b) a second base oil
component in the amount of about 0.1 weight % to about 80 weight %
based on the total weight of the oil composition, wherein the
second base oil component comprises one or more of a
polyalphaolefin (PAO) base stock, Group II base stock, Group III
base stock, Group V base stock, GTL base stock, alkylated benzene
base stock, and ester base stock; wherein the composition has a
kinematic viscosity at 100.degree. C. of about 7.6 cSt or less, a
Noack volatility at 250.degree. C. of less than about 10%, and a
viscosity index of at least about 90.
[0012] Provided herein is an internal combustion engine oil, such
as a compression-ignition engine oil or a spark-ignition engine
oil, comprising a lubricant oil composition provided herein.
4 DETAILED DESCRIPTION
4.1 Definitions
[0013] An "alkyl" is a saturated straight chain or branched
non-cyclic hydrocarbon having, for example, from 18 to 40 carbon
atoms, 18 to 32 carbon atoms, 20 to 24 carbon atoms, 18 carbon
atoms, 20 carbon atoms, or 32 carbon atoms. Representative alkyls
include, for example, -methyl, -ethyl, -n-propyl, -n-butyl,
-n-pentyl and, -n-hexyl; while branched alkyls include, for
example, -isopropyl, -sec-butyl, -iso-butyl, -tert-butyl,
-iso-pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
2,3-dimethylbutyl, Guerbet alkyl and the like.
[0014] A "Guerbet alkyl" is a beta-branched alkyl of the general
formula: (C.sub.n-C.sub.m)alkyl-CH[(C.sub.(n-2)-C.sub.(m-2
))alkyl]-CH.sub.2--, wherein n.ltoreq.m, and wherein n and m are
independently integers equal or greater than 6, but equal or less
than 18, resulting in a (C.sub.2n-C.sub.2m) Guerbet alkyl. For
example, in a (C.sub.18-C.sub.32) Guerbet alkyl, n is 9 and m is
18. In certain embodiments, the (C.sub.n-C.sub.m)alkyl and
(C.sub.(n-2)-C.sub.(m-2))alkyl groups of the Guerbet alkyl may be
branched. Representative Guerbet alkyls include, for example,
2-butyl-octanyl, 2-hexyl-decanyl, 2-octyl-dodecanyl,
2-decyl-tetradecanyl, and 2-dodecyl-hexadecanyl.
[0015] A "cycloalkyl" is a saturated cyclic alkyl having, for
example, from 3 to 12 carbon atoms or 5 to 40 carbon atoms, having
a single cyclic ring or multiple condensed or bridged rings.
Representative alkyls include, for example, single ring structures
such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, and the like, or multiple or bridged ring
structures such as adamantyl and the like.
[0016] An "aryl" is an aromatic carbocyclic group having, for
example, from 6 to 40 carbon atoms having a single ring (e.g.,
phenyl) or multiple condensed rings (e.g., naphthyl or anthryl).
Representative aryls include, for example, phenyl, naphthyl, and
the like.
[0017] An "aralkyl" is an aryl-substituted alkyl group having, for
example, an aryl substituted (C.sub.7-C.sub.9)alkyl. Representative
aralkyls include, for example, benzyl, diphenylmethyl,
triphenylmethyl, phenylethyl, phenylbutyl, and diphenylethyl.
[0018] A "base oil" and "base stock" as referred to herein is to be
considered consistent with the definitions as stated in API BASE
OIL INTERCHANGEABILITY GUIDELINES FOR PASSENGER CAR MOTOR OILS AND
DIESEL ENGINE OILS, July 2009 Version--APPENDIX E. According to
Appendix E, base oil is the base stock or blend of base stocks used
in an API-licensed oil. Base stock is a lubricant component that is
produced by a single manufacturer to the same specifications
(independent of feed source or manufacturer's location) that meets
the same manufacturer's specification and that is identified by a
unique formula, product identification number, or both.
4.2 Lubricant Oil Compositions
[0019] Provided herein is a lubricant oil composition comprising
[0020] (a) a first base oil component in the amount of about 1
weight % to about 50 weight % based on the total weight of the oil
composition, wherein the first base oil component comprises a
compound of Formula I
[0020] ##STR00002## wherein R is (C.sub.18-C.sub.40)alkyl,
(C.sub.5-C.sub.40)cycloalkyl, (C.sub.5-C.sub.40)aryl,
(C.sub.7-C.sub.9)aralkyl; wherein the aralkyl is optionally
substituted with (C.sub.1-C.sub.36)alkyl, or
(C.sub.6-C.sub.40)alkenyl; and
[0021] (b) a second base oil component in the amount of about 0.1
weight % to about 80 weight % based on the total weight of the oil
composition, wherein the second base oil component comprises one or
more of a polyalphaolefin (PAO) base stock, Group II base stock,
Group III base stock, Group V base stock, GTL base stock, alkylated
benzene base stock, and ester base stock;
wherein the composition has a kinematic viscosity at 100.degree. C.
of about 7.6 cSt or less, a Noack volatility at 250.degree. C. of
less than about 10%, and a viscosity index of at least about
90.
[0022] In one embodiment, the lubricant oil composition has a
kinematic viscosity at 100.degree. C. of about 7.6 cSt or less,
about 7.0 cSt or less, about 6.5 cSt or less, about 6.0 cSt, about
5.5 cSt or less, or about 5.0 cSt or less, a Noack volatility at
250.degree. C. of less than about 10%, less than about 9%, less
than about 8%, less than about 7%, or less than about 6%, and a
viscosity index of at least about 90, at least about 95, at least
about 100, at least about 105, at least about 110, at least about
115, or at least about 120.
[0023] Provided herein is an internal combustion engine oil, such
as an compression-ignition engine oil and a spark-ignition engine
oil, comprising a lubricant oil composition provided herein.
[0024] In one embodiment, the lubricant oil composition provided
herein has one or more of the following properties selected from
the group consisting of oxidation resistance, swell
characteristics, deposit performance, reserve alkalinity, rust
preventing quality, and levels of ash-forming compound, improved as
compared to an oil composition comprising a second base oil
component as provided herein, but not comprising the first base oil
component as provided herein.
[0025] The kinematic viscosity of the lubricant oil compositions
provided herein may be determined by any suitable method known to
the person of ordinary skill in the art. In one embodiment, the
kinematic viscosity is determined using a standardized method, such
as ASTM D445, 2012, "Standard Test Method for Kinematic Viscosity
of Transparent and Opaque Liquids (and Calculation of Dynamic
Viscosity)," ASTM International, West Conshohocken, Pa., 2012, DOI:
10.1520/D0445-12, www.astm.org.
[0026] The Noack volatility of the lubricant oil compositions
provided herein may be determined by any suitable method known to
the person of ordinary skill in the art. In one embodiment, the
kinematic viscosity is determined using a standardized method, such
as ASTM D5800, 2010, "Standard Test Method for Evaporation Loss of
Lubricating Oils by the Noack Method," ASTM International, West
Conshohocken, Pa., 2010, DOI: 10.1520/D5800-10, www.astm.org.
[0027] The viscosity index of the lubricant oil compositions
provided herein may be determined by any suitable method known to
the person of ordinary skill in the art. In one embodiment, the
viscosity index is determined using a standardized method, such as
ASTM D2270, 2010e1, "Standard Practice for Calculating Viscosity
Index From Kinematic Viscosity at 40 and 100.degree. C.," ASTM
International, West Conshohocken, Pa., 2010, DOI:
10.1520/D2270-10E01, www.astm.org.
[0028] In one embodiment, the lubricant oil composition provided
herein has a CCS viscosity of less than 3500 cP at -35.degree. C.
as determined by ASTM D5293, and an HTHS viscosity of less than 2.6
mPas at 150.degree. C. as determined by ASTM D4683. In a further
embodiment, the lubricant oil composition provided herein has a
kinematic viscosity of from about 20 to about 80 cSt, or from about
30 to about 40 cSt as measured at 40.degree. C. in accordance with
the ASTM D445, for example, ASTM D445, 2012, "Standard Test Method
for Kinematic Viscosity of Transparent and Opaque Liquids (and
Calculation of Dynamic Viscosity)," ASTM International, West
Conshohocken, Pa., 2012, DOI: 10.1520/D0445-12, www.astm.org. In
another embodiment, the lubricant oil composition provided herein
shows a kinematic viscosity range from at 100.degree. C. from about
4 to about 6 cSt.
4.2.1 First Base Oil Component
[0029] Provided herein is a lubricant oil composition comprising a
first base oil component in the amount of about 1 weight % to about
50 weight % based on the total weight of the oil composition,
wherein the first base oil component comprises a compound of
Formula I
##STR00003##
wherein R is (C.sub.18-C.sub.40)alkyl,
(C.sub.5-C.sub.40)cycloalkyl, (C.sub.5-C.sub.40)aryl,
(C.sub.7-C.sub.9)aralkyl; and wherein the aralkyl is optionally
substituted with (C.sub.1-C.sub.36)alkyl or
(C.sub.6-C.sub.40)alkenyl.
[0030] In one embodiment, the first base oil component has a
kinematic viscosity at 100.degree. C. of equal or less than about
7.0 cSt, a Noack volatility at 250.degree. C. of less than about
8%, and a viscosity index equal or higher than about 80. In another
embodiment, the first base oil component has a kinematic viscosity
at 100.degree. C. of about 6.0 cSt or less. In one embodiment, the
first base oil component has a pour point of about 0.degree. C. or
less.
[0031] In another embodiment, the first base oil component has a
kinematic viscosity at 100.degree. C. of equal or less than about
7.0 cSt, equal or less than about 6.5 cSt, equal or less than about
6.0 cSt, equal or less than about 5.5 cSt, equal or less than about
5.0 cSt, or from about 5.0 cSt to about 7.0 cSt, a Noack volatility
at 250.degree. C. of less than about 8%, less than about 12%, less
than about 11%, less than about 10%, less than about 9%, less than
about 7%, less than about 6%, less than about 5%, or less than
about 4%, and a viscosity index equal or higher than about 80, or
higher than about 85, or higher than about 90, or higher than about
95, or higher than about 100.
[0032] The kinematic viscosity, Noack volatility or viscosity index
of the first base oil component of the lubricant oil composition
provided herein may be determined by any suitable method known to
the person of ordinary skill in the art. In one embodiment, the
kinematic viscosity, Noack volatility and viscosity index is
determined using the standardized methods referenced in Section 4.2
hereinabove.
[0033] Further provided herein is a lubricant oil composition
comprising a first base oil component in the amount of about 1 wt %
to about 40 wt %, about 1 wt % to about 30 wt %, about 1 wt % to
about 20 wt %, about 1 wt % to about 10 wt %, about 5 wt % to about
50 wt %, about 10 wt % to about 50 wt %, about 20 wt % to about 50
wt %, about 30 wt % to about 50 wt %, about 40 wt % to about 50 wt
%, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %,
or about 10 wt % to about 40 wt %, based on the total weight of the
oil composition. In one embodiment, the lubricant oil composition
comprises a first base oil component in the amount of about 20 wt %
to about 30 wt % based on the total weight of the oil
composition.
[0034] In one embodiment, the first base oil component comprises a
compound of Formula I, wherein R is (C.sub.18-C.sub.32)alkyl. In
one embodiment, the first base oil component comprises a compound
of Formula I, wherein R is (C.sub.20-C.sub.24)alkyl. In one
embodiment, the first base oil component comprises a compound of
Formula I, wherein R is C.sub.18 alkyl. In one embodiment, the
first base oil component comprises a compound of Formula I, wherein
R is C.sub.20 alkyl. In one embodiment, the first base oil
component comprises a compound of Formula I, wherein R is C.sub.32
alkyl.
[0035] In one embodiment, the first base oil component comprises a
mixture of two or more compounds of Formula I. For example, the
first base oil component comprises a mixture of 2, 3, 4, 5, 6, 7,
8, 9, or 10 or more compounds of Formula I. In one embodiment, the
first base oil component comprises a mixture of two or more
compounds of Formula I, wherein at least one compound is a compound
of Formula I, wherein R is a C.sub.20 alkyl and at least one
compound is a compound of Formula I, wherein R is a C.sub.24 alkyl.
In another embodiment, the first base oil component comprises a
mixture of two or more compounds of Formula I, wherein at least one
compound is a compound of Formula I, wherein R is a C.sub.18 alkyl
and at least one compound is a compound of Formula I, wherein R is
a (C.sub.20-C.sub.24)alkyl.
[0036] In one embodiment, the first base oil component comprises a
compound of Formula I, wherein R is (C.sub.18-C.sub.32) Guerbet
alkyl. In one embodiment, the first base oil component comprises a
compound of Formula I, wherein R is C.sub.18 Guerbet alkyl. In one
embodiment, the first base oil component comprises a compound of
Formula I, wherein R is C.sub.20 Guerbet alkyl. In one embodiment,
the first base oil component comprises a compound of Formula I,
wherein R is C.sub.24 Guerbet alkyl. In one embodiment, the first
base oil component comprises a compound of Formula I, wherein R is
C.sub.28 Guerbet alkyl. In one embodiment, the first base oil
component comprises a compound of Formula I, wherein R is C.sub.32
Guerbet alkyl.
[0037] In one embodiment, the first base oil component comprises a
mixture of two or more compounds of Formula I, wherein R for each
of the two or more compounds is independently selected from
(C.sub.18-C.sub.40)alkyl, (C.sub.5-C.sub.40)cycloalkyl,
(C.sub.5-C.sub.40)aryl, (C.sub.7-C.sub.9)aralkyl,
(C.sub.18-C.sub.32)alkyl, (C.sub.20-C.sub.24)alkyl, C.sub.18 alkyl,
C.sub.20 alkyl, C.sub.32 alkyl, (C.sub.18-C.sub.32) Guerbet alkyl,
C.sub.18 Guerbet alkyl, C.sub.20 Guerbet alkyl, C.sub.24 Guerbet
alkyl, C.sub.28 Guerbet alkyl, or C.sub.32 Guerbet alkyl.
[0038] In one embodiment, the compound of Formula I is a compound,
wherein R is C.sub.1-C.sub.300 linear alkyl, or a C.sub.12-C.sub.32
linear alkyl or a C.sub.18-C.sub.32 branched alkyl. In one
embodiment, the compound of Formula I is a compound, wherein R is a
C.sub.3 alkyl, a C.sub.4 alkyl, a C.sub.5 alkyl, a C.sub.6 alkyl, a
C.sub.8 alkyl, a C.sub.10 alkyl, a C.sub.12 alkyl, a C.sub.14
alkyl, a C.sub.16 alkyl, or a C.sub.18 alkyl. In another
embodiment, the first base oil component is a mixture of
C.sub.10-C.sub.14 alkyl naphthalenes, or a mixture of
C.sub.6-C.sub.18 alkyl naphthalenes, or the mono C.sub.3, C.sub.4,
C.sub.5, C.sub.6, C.sub.8, C.sub.10, C.sub.12, C.sub.14, C.sub.16,
C.sub.18 alkyl naphthalene and mixtures thereof, or the
alkyl-derivatives of monomethyl, dimethyl, ethyl, diethyl, or
methylethyl naphthalenes, or mixtures thereof.
[0039] In a further embodiment, the compound of Formula I is a
compound, wherein R is a C.sub.10-C.sub.300 branched alkyl, or
C.sub.24-C.sub.56 branched alkyl.
[0040] The compounds Formula I can be prepared by methods known to
the person of ordinary skill in the art. In particular, suitable
methods involve the alkylation of naphthalene with an olefin,
alcohol, alkyl halide, or other alkylating agents known to those of
ordinary skill in the art in the presence of a catalyst. The
catalyst is a suitable Lewis acid or super acid. Suitable Lewis
acids are, for example, boron trifluoride, iron trichloride, tin
tetrachloride, zinc dichloride, and antimony pentafluoride.
Furthermore, acidic clays, silica, or alumina are suitable. See for
example U.S. Pat. Nos. 4,604,491 and 4,764,794, all of which are
incorporated herein by reference in their entireties. Suitable
super acid catalysts include trifluoromethane sulfonic acid,
hydrofluoric acid or trifluoromethylbenzene sulfonic acid. Other
suitable catalysts include acidic zeolite catalysts, such as
Zeolite Beta, Zeolite Y, ZSM-5, ZSM-35, and USY. In one embodiment,
alkylated naphthalenes may be obtained by alkylating naphthalene
with an olefin using aluminum chloride as a catalyst. The use of a
co-catalyst such as nitromethane or nitrobenzene to promote the
reaction is also suitable. See, for example, U.S. Pat. No.
2,754,548, which is incorporated herein by reference in its
entirety. In another embodiment, alkylated naphthalenes may be
obtained by alkylating naphthalene with an olefin using
trifluoromethane sulfonic acid as a catalyst.
[0041] In one embodiment, compounds other than naphthalene may be
alkylated to provide suitable alkylated naphthalenes. In a
particular embodiment, the addition of longer chain alkyl groups,
e.g., about C.sub.6 to C.sub.30, to short chain alkylated
naphthalenes, e.g., methyl naphthalene, ethyl naphthalene, propyl
naphthalene, butyl naphthalene, isopropyl naphthalene, and
diisopropyl naphthalene, is suitable.
[0042] Suitable poly-alphaolefins may be derived from alphaolefins,
i.e., alk-1-enyls, which include but are not limited to C.sub.2 to
C.sub.32 alphaolefins, C.sub.12 to C.sub.18 alphaolefins, C.sub.10
to C.sub.32 alphaolefins, such as 1-decene, 1-dodecene, and
1-octadecene. In one embodiment, useful polyalphaolefins are
poly-1-decene or poly-1-dodecene, poly-1-hexadecene or
poly-1-hexadecenedecene, poly-1-octadecene or
poly-1-octadecene.
[0043] Suitable alpha-olefins useful in this process for
introducing linear alkyl groups are, for example, 1-dodecene,
1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,
1-docosene, 1-tetracosene or 1-triacontene, .alpha.-methyl styrene
or mixtures thereof. Mixtures of the alpha-olefins, e.g., mixtures
of C.sub.12-C.sub.20, or C.sub.14-C.sub.18 olefins or
C.sub.16-C.sub.18 olefins, are also useful. These alpha-olefins are
largely items of commerce or are made by the telomerization of
ethylene by known methods. Straight chain alkenes containing an
internal double bond may be for example 5-dodecene or 9-tricosene.
These alkenes are also largely items of commerce.
[0044] Branched alkyl groups can be prepared from oligomerization
of small olefins, such as C.sub.5-C.sub.24 alpha- or
internal-olefins. When the branched alkyl group is very large (that
is 8 to 300 carbons), usually only one or two of such alkyl groups
are attached to the naphthalene core. The alkyl groups on the
naphthalene ring can also be mixtures of the above alkyl groups. In
one embodiment, mixed alkyl groups are advantageous, because they
provide improvement of pour points and low temperature fluid
properties, such as low temperature fluidity, stability and
solvency.
[0045] Other useful alkylating agents, which may be used, include
alcohols (inclusive of monoalcohols, dialcohols, trialcohols, etc.)
such as hexanols, heptanols, octanols, nonanols, decanols,
undecanols, dodecanols and octadecanols; and alkyl halides such as
hexyl chlorides, octyl chlorides, dodecyl chlorides; and higher
homologs. Also useful for preparing compounds of Formula I are
various branched Guerbet alcohols containing up to 32 carbon atoms
and sold under the trade name ISOFOL.RTM. by Sasol. Examples of
useful alcohols include ISOFOL.RTM. 18 T, 18E, 20, 24, 28, and
32.
[0046] Other non-limiting examples of alkylating agents are those
derived from uncrosslinked polyisoprenes or polybutadienes, e.g.,
KRASOL.RTM. LB 3000 having a molecular weight M.sub.n of 2300-3000,
polyisobutylenes e.g., TPC 535(MW 350), TPC 595(MW 950), TPC
5230(MW 2300), TPC 150(MW 500), TPC 137(MW 350), TPC 160(MW 600),
TPC 168(MW 680), TPC 175(MW 750), TPC 181(MW 810), TPC 1105(MW
1000), TPC 1160(MW 1600), and TPC 1285(MW 3000) from Texas
Petrochemicals, polybutenes. Other examples include L-14(Mn 370),
L-50(Mn 455), L-65(Mn 435), L-100(Mn 510), H-15(Mn 600), H-25(Mn
670), H-35(Mn 725), H-40(Mn 750), H-50(Mn 815), H-100(Mn 940),
H-300(Mn 1330), H-1500(Mn 2145), and H-1900(Mn 2270) from AMOCO,
polybutenes PB 24 (Mn 950), PB 32(Mn 1200-1375), PB 122(Mn 2225),
PB 124(Mn 2400), and PB 128(Mn 2600) from Soltex. Still other
examples include copolymers of mono- and diolefins, for example
propylene/butadiene copolymers, styrene/butadiene copolymers or
acrylonitrile/butadiene copolymers, terpolymers such as
styrene/butadiene/alkylacrylate, terpolymers or
styrene/butadiene/methacrylate terpolymers or
acrylonitrile/alkylmethacrylate/butadiene terpolymers, terpolymers
with ethylene, propylene and a diene, typically hexadiene,
dicyclopentadiene, norbornadiene or ethylidenenorbornene, block
copolymers of styrene, such as styrene/butadiene/styrene or
styrene/isoprene/styrene, graft copolymers of styrene or
.alpha.-methylstyrene on polybutadiene, polybutadiene containing
terminal hydroxyl groups, e.g., KRASOL.RTM. LBH 3000, linear
polycyclopentadienes or cyclic olefins polymerized by ring-opening
metathesis, e.g., polyoctenamers, for example VESTENAMER.RTM. L
3000 (Huls) having a molecular weight M.sub.n of about 2300-3000,
or polynorbornenes, e.g., of the NORSOREX.RTM. type (Nippon Zeon),
as well as all polyunsaturated polymeric basic compounds grafted
with cyclopentadiene by the Diels-Alder method of the
above-mentioned type. It is particularly advantageous to use homo-
and copolymers of diolefins, for example butadiene, isoprene or
pentadiene, and also of cyclic, optionally polynuclear, diolefins,
typically dicyclopentadiene or norbornene as well as ring-opening
polymerized cyclic olefins, e.g., polyoctenamers or
polynorbornenes.
[0047] Typically the compounds of Formula I, such as alkyl
naphthalenes may be prepared by alkylation of naphthalene or short
chain alkyl naphthalene, such as methyl or dimethyl naphthalene,
with olefins, alcohols or alkylchlorides of 6 to 24 carbons over
acidic catalyst inducing typical Friedel Crafts catalysts. Typical
Friedel-Crafts catalysts are AlCl.sub.3, BF.sub.3, HT, zeolites,
amorphous alumniosilicates, acid clays, acidic metal oxides or
metal salts, or USY. See U.S. Pat. No. 5,034,563, U.S. Pat. No.
5,516,954, and U.S. Pat. No. 6,436,882, all of which are
incorporated herein by reference in their entireties.
[0048] An .alpha.-olefin or internal olefin can be oligomerized in
the presence of promoted catalyst to give predominantly olefin
dimer and higher oligomers. Once the reaction has gone to
completion, an aromatic composition containing one or more
naphthalene compound is reacted with the oligomers, in the presence
of the same catalyst, to give alkylated aromatic base oil
components in high yield.
[0049] The naphthalene or mono substituted short chain alkyl
naphthalenes can be derived from any conventional
naphthalene-producing process from petroleum, petrochemical process
or coal process or source stream. Naphthalene-containing feeds can
be made from aromatization of suitable streams available from the
F-T process. For example, aromatization of olefins or paraffins can
produce naphthalene or naphthalene-containing component
(DE84-3414705, US20060138024 A1, both of which are incorporated
herein in their entireties). Many medium or light cycle oils from
petroleum refining processes contain significant amounts of
naphthalene, substituted naphthalenes or naphthalene derivatives.
Indeed, substituted naphthalenes recovered from whatever source, if
possessing up to about three alkyl carbons can be used as raw
material to produce alkylnaphthalene for lubricant oil compositions
provided herein. Furthermore, alkylated naphtahlenes of Formula I
recovered from whatever source or processing can be used the
lubricant oil compositions provided herein, provided they possess
kinematic viscosities, viscosity index and Noack volatility as
previously recited.
4.2.2 Second Base Oil Component
[0050] Provided herein is lubricant oil composition comprising a
second base oil component in the amount of about 0.1 weight % to
about 80 weight % based on the total weight of the oil composition,
wherein the second base oil component comprises one or more of a
polyalphaolefin (PAO) base stock, Group II base stock, Group III
base stock, Group V base stock, GTL base stock, alkylated benzene
base stock, and ester base stock.
[0051] In one embodiment, the second base oil component comprises a
polyalphaolefin (PAO) base stock. In one embodiment, the second
base oil component comprises a Group II base stock. In one
embodiment, the second base oil component comprises a Group III
base stock. In one embodiment, the second base oil component
comprises a Group V base stock. In one embodiment, the second base
oil component comprises a GTL base stock. In one embodiment, the
second base oil component comprises an alkylated benzene base
stock. In one embodiment, the second base oil component comprises
an ester base stock.
[0052] Further provided herein is a lubricant oil composition
comprising a second base oil component in the amount of about 0.1
wt % to about 70 wt %, about 0.1 wt % to about 60 wt %, about 0.1
wt % to about 50 wt %, about 0.1 wt % to about 40 wt %, about 0.1
wt % to about 30 wt %, about 5 wt % to about 80 wt %, about 10 wt %
to about 80 wt %, about 20 wt % to about 80 wt %, about 30 wt % to
about 80 wt %, about 40 wt % to about 80 wt %, about 50 wt % to
about 80 wt %, about 60 wt % to about 80 wt %, about 70 wt % to
about 80 wt %, about 10 wt % to about 20 wt %, about 20 wt % to
about 30 wt %, or about 10 wt % to about 40 wt %, based on the
total weight of the oil composition. In one embodiment, the
lubricant oil composition comprises a first base oil component in
the amount of about of 70 wt % to about 80 wt % based on the total
weight of the oil composition.
[0053] Further provided herein is a lubricant oil composition
comprising a first base oil component in the amount of about 1 wt %
to about 40 wt %, about 1 wt % to about 30 wt %, about 1 wt % to
about 20 wt %, about 1 wt % to about 10 wt %, about 5 wt % to about
50 wt %, about 10 wt % to about 50 wt %, about 20 wt % to about 50
wt %, about 30 wt % to about 50 wt %, about 40 wt % to about 50 wt
%, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %,
or about 10 wt % to about 40 wt %, based on the total weight of the
oil composition, and a second base oil component in the amount of
about 0.1 wt % to about 70 wt %, about 0.1 wt % to about 60 wt %,
about 0.1 wt % to about 50 wt %, about 0.1 wt % to about 40 wt %,
about 0.1 wt % to about 30 wt %, about 5 wt % to about 80 wt %,
about 10 wt % to about 80 wt %, about 20 wt % to about 80 wt %,
about 30 wt % to about 80 wt %, about 40 wt % to about 80 wt %,
about 50 wt % to about 80 wt %, about 60 wt % to about 80 wt %,
about 70 wt % to about 80 wt %, about 10 wt % to about 20 wt %,
about 20 wt % to about 30 wt %, or about 10 wt % to about 40 wt %,
based on the total weight of the oil composition.
[0054] As set forth in API BASE OIL INTERCHANGEABILITY GUIDELINES
FOR PASSENGER CAR MOTOR OILS AND DIESEL ENGINE OILS, July 2009
Version--APPENDIX E, Group I base stocks contain less than about 90
percent saturates, tested according to ASTM D2007 and/or greater
than about 0.03 percent sulfur, tested according to ASTM D1552,
D2622, D3120, D4294, or D4927; and a viscosity index of greater
than or equal to about 80 and less than about 120, tested according
to ASTM D2270. Group II base stocks contain greater than or equal
to about 90 percent saturates; less than or equal to about 0.03
percent sulfur; and a viscosity index greater than or equal to
about 80 and less than about 210. Group III base stocks contain
greater than or equal to 90 percent saturates; less than or equal
to about 0.03 percent sulfur; and a viscosity index greater than or
equal to about 120. Group IV base stocks are polyalphaolefins
(PAOs). Group V base stocks include all other base stocks not
included in Group I, II, III, or IV, such as naphthenics, esters,
GTL and polyglycols.
[0055] The polyalphaolefin ("PAO") is a polymer made by
polymerizing alphaolefin. Base stock 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.
[0056] The PAO base stock may be made by any method known in the
art. See, for example, U.S. Pat. No. 3,149,178; U.S. Pat. No.
3,382,291; U.S. Pat. No. 3,742,082; U.S. Pat. No. 3,769,363; U.S.
Pat. No. 3,876,720; U.S. Pat. No. 4,149,178; U.S. Pat. No.
4,218,330; U.S. Pat. No. 4,239,930; U.S. Pat. No. 4,367,352; U.S.
Pat. No. 4,413,156; U.S. Pat. No. 4,434,408; U.S. Pat. No.
4,910,355; U.S. Pat. No. 4,967,032; U.S. Pat. No. 4,926,004; U.S.
Pat. No. 4,956,122; U.S. Pat. No. 4,914,254; U.S. Pat. No.
4,827,073; U.S. Pat. No. 4,827,064; U.S. Pat. No. 5,068,487; all of
which are incorporated herein by reference in their entireties. PAO
fluids may be optionally substituted by, e.g., carboxylic acid
esters.
[0057] The average molecular weight of the PAO base stock to be
used in the lubricate oil composition provided herein varies from
about 250 Da to about 10,000 Da, or from about 300 Da to about
3,000 Da, with a kinematic viscosity varying from about 3 cSt to
about 10 cSt at 100.degree. C.
[0058] In one embodiment, the concentrations of a compound of
Formula I, in particular, an alkylated naphthalene (AN), in the PAO
base stock can vary from about 1 wt % to less than about 50 wt %,
or from about 5 wt % to about 45 wt %, or from about 5 wt % to
about 25 wt % of the total weight of the lubricant oil
composition.
[0059] In one embodiment, the PAO base stock comprises a carboxylic
acid ester in the amount of less than about 10 wt % of the total
weight of the lubricant oil composition. In a certain embodiment,
the ester is an ester of monohydric alcohols, having about 9 to 20
carbon atoms, and of dibasic carboxylic acids, having from about 6
to 12 carbon atoms, such as adipic or azelaic acid.
[0060] In one embodiment, the second base oil component is a PAO
obtained by the process disclosed in US 2013/0090273, which is
incorporated herein by reference in its entirety.
[0061] Group II and/or Group III base oils are complex mixtures of
hundreds of isomers of different carbon number (generally
n-paraffins, cycloparaffins, and naphthenics) and contain some
small amount of unsaturation (generally less than 10%) as well as
other trace impurities such a sulfur and nitrogen. Group II and/or
Group III base oils may be prepared, for example, in accordance
with U.S. Pat. No. 5,935,417 and U.S. Pat. No. 5,993,644; both of
which are incorporated herein by reference in their entireties.
Typically, processes commonly used to produce conventional mineral
base oil stocks known in the art are first applied to the crude
oil. For example, the crude oil may be subjected to distillation,
solvent dewaxing, and solvent extraction of aromatic compounds. To
produce Group II and Group III base oils, the oil is then subjected
to further apart processing referred to in the art as
hydrotreating, hydrocracking, hydroisomerization and hydrofining.
In such a process, the oil is mixed with hydrogen in a reactor in
the presence of a catalyst to hydrogenate most of the double bonds
or unsaturated hydrocarbons. Depending on the severity of the
hydrotreatment, aromatic molecules still remaining after
conventional solvent extraction are also hydrogenated to saturated
ring structures. In addition, the saturated ring structures can
also be ring opened to linear molecules. Most of the sulfur and
nitrogen impurities are converted to hydrogen sulfide and ammonia
which are removed. In some instances, the feed for this
hydrotreating process is not a conventional base oil at all, but
the waste products isolated during solvent dewaxing. The result is
a base oil which has more n-paraffins and isoparaffins than
traditional base oils, low unsaturation (generally less than 2%),
very low levels of sulfur and nitrogen impurities, and a high
viscosity index. Group III base oils are subjected to a more severe
hydrotreating process than Group II base oils.
[0062] Gas to Liquids ("GTL") base stock can be obtained by a
process that converts natural gas into synthetic oil, which can
then be further processed into fuels and other hydrocarbon based
products. This process results in extremely pure synthetic crude
oil that is virtually free of contaminants such as sulfur,
aromatics and metals, which in turn can be refined into products,
such as diesel fuel, and other petroleum or specialty products.
Typical GTL base stock properties are listed in TABLE 1 below in
comparison with typical Group III and PAO base stocks.
TABLE-US-00001 TABLE 1 Typical Typical Properties Group III PAO GTL
Kinematic viscosity cSt @ 100.degree. C. 3.9 4.0 3.8 Viscosity
Index 143 124 140 Noack volatility wt % off 15.6 12.7 14.5 max Pour
point, .degree. C. -18 <-64 -21 Sulfur, ppm <4 <1
<1
[0063] An alkylated benzene base stock comprises alkylated benzene
of Formula II with kinematic viscosity at 100.degree. C. of 1.5 to
6.0 cSt, a viscosity index of 0 to 200 and pour point of 0.degree.
C. or less, or -15.degree. C. or less, or -25.degree. C. or less,
or -35.degree. C. or less, or -60.degree. C. or less.
[0064] The alkylated benzene for use as a second base oil component
is a compound of Formula II
##STR00004##
wherein x=1 to 6, or 1 to 5, or 1 to 4. When the compound of
Formula II is a monoalkylated benzene, R can be linear C.sub.10 to
C.sub.30 alkyl group or a C.sub.10-C.sub.300 branched alkyl group,
or a C.sub.10-C.sub.100 branched alkyl group, or a
C.sub.15-C.sub.50 branched alkyl group. When n is 2 or greater than
2, one or two of the alkyl groups can be a C.sub.1 to C.sub.5 alkyl
group, or C.sub.1-C.sub.2 alkyl group. The other alkyl group or
groups can be any combination of linear C.sub.10-C.sub.30 alkyl
group, or branched C.sub.10 to C.sub.300 alkyl group, or
C.sub.15-C.sub.50 branched alkyl group. These branched large alkyl
radicals can be prepared from the oligomerization or polymerization
of C.sub.3 to C.sub.20, internal or alpha-olefins or mixture of
these olefins. The total number of carbons in the alkyl
substituents ranges from C.sub.10 to C.sub.300. In one embodiment,
the alkylated benzene stock may be prepared according to U.S. Pat.
No. 6,071,864, U.S. Pat. No. 6,491,809, or EP 0,168,534; all of
which are incorporated herein by reference in their entireties.
[0065] In one embodiment, the molar ratio of aromatic compound to
.alpha.-olefin oligomers is from about 0.05:1 to about 20:1. In
another embodiment, the ratio of aromatic compound to
.alpha.-olefin oligomers is from about 0.1:1 to about 8:1.
[0066] In one embodiment, the alkylaromatic fluids used in the
lubricant oil composition provided herein have pour points of
0.degree. C. or less. In another embodiment, the alkyl methyl
benzene fluid was prepared according to procedures described in
U.S. Pat. No. 6,071,864, which is incorporated herein by reference
in its entirety, starting from the oligomerization of a mixture of
C.sub.8, C.sub.10 and C.sub.12 linear alpha olefins, over a
promoted BF.sub.3 catalyst to produce a product which is reacted
with toluene over the same catalyst at same reaction
temperature.
[0067] A dialkylbenzene ("DAB") as described in U.S. Pat. No.
6,491,809 can also be used in the lubricant oil composition
provided herein. DAB can be prepared by repeated alkylation of
benzene, e.g., alkylation of benzene to give mono-alkylbenzene,
followed by further alkylation of this mono-alkylbenzene in the
same reactor or in a separate reactor. Alkylbenzenes can also be
obtained from many detergent alkylbenzene processes. In these
processes, linear alkylbenzene ("LAB") is produced by alkylation of
benzene over alkylation catalyst. The mono-alkyl LAB is used as raw
material for detergent production.
[0068] Further, it has been found that the hydrogenated analogues
of the alkylated naphthalene or alkylated benzene described above
are also effective base oil stocks, and hydrodewaxed or
hydroisomerized/catalytic (and/or solvent) dewaxed wax derived base
stocks/base oils. Further, it has been found that the alkylated
naphthalene or alkylated benzene fluids can provide un-expected
improvement of oxidation stability of the blends with GTL fluids.
This oxidative stability improvement can be demonstrated by longer
RBOT (ASTM D2272 method) or other oxidation test methods. Further,
it has been found that the alkylated naphthalene or alkylated
benzene fluids can improve the polarity of the blends with GTL
fluids. This higher polarity of the blend indicates a better
solubility of additives and other polar components formed during
oil service. Thus, the blend with these alkylated aromatic fluids
can provide higher level of finished lubricant performance.
[0069] In one embodiment, the second base oil component is an
ester. Additive solvency and seal compatibility characteristics may
be secured by the use of esters, such as the esters of dibasic
acids with monoalkanols and the polyol esters of mono-carboxylic
acids. Esters of the former type include, for example, the esters
of dicarboxylic acids such as phthalic acid, succinic acid, alkyl
succinic acid, alkenyl succinic acid, maleic acid, azelaic acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid;
with a variety of alcohols such as butyl alcohol, hexyl alcohol,
dodecyl alcohol, 2-ethylhexyl alcohol, etc. In one embodiment, the
ester is dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,
dioctyl phthalate, didecyl phthalate, or dieicosyl sebacate.
[0070] In one embodiment, the synthetic esters are those full or
partial esters which are obtained by reacting one or more
polyhydric alcohols (e.g., the hindered polyols such as the
neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane,
2-methyl-2-propyl-1,3-propanediol, trimethylol propane,
pentaerythritol and dipentaerythritol) with alkanoic acids
containing at least about 4 carbon atoms (e.g., C.sub.5 to C.sub.30
acids such as saturated straight chain fatty acids including
caprylic acid, capric acid, lauric acid, myristic acid, palmitic
acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid).
[0071] Suitable synthetic ester components include the esters of
trimethylol propane, trimethylol butane, trimethylol ethane,
pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from about 5 to about 10 carbon
atoms.
[0072] In one embodiment, the ester is an ester of a
phosphorus-containing acid, such as tricresyl phosphate, trioctyl
phosphate, or diethyl ester of decanephosphonic acid.
4.2.3 Additives
[0073] In one embodiment, the engine oil composition comprises a
lubricant oil composition as provided herein, which further
comprises one or more additives. In a particular embodiment, the
lubricant oil compositions provided comprise one or more additives
and are formulated as internal combustion engine oil
compositions.
[0074] In one embodiment, the lubricant oil composition further
comprises one or more additives in an amount up to about 20 wt %,
or up to about 5%, or from about 0.001 wt % to about 10 wt %, of
the total weight of the lubricant oil composition.
[0075] In some embodiments, the lubricant oil compositions provided
herein further comprise one or more additives, wherein the additive
is a detergent, a dispersant, an antioxidant, a pour point
depressant, a viscosity index (VI) improver, an anti-wear agent, an
extreme pressure additive, a friction modifier, a demulsifier, an
antifoamant, a corrosion inhibitor, a seal swell control additive,
or a metal deactivator. In a certain embodiment, the lubricant oil
compositions provided herein further comprise one or more
additives, wherein the additive is a detergent, a dispersants, a
antioxidant, a anti-wear agent, or a VI improver.
[0076] An effective amount of one or more additives can be added
to, blended into or admixed with the base stock to meet one or more
formulated product specifications, such as those relating to a
lubricating oil composition for diesel engines, internal combustion
engines, automatic transmissions, turbine or jet, hydraulic oil,
industrial oil, etc., as is known to the person of ordinary skill
in the art. Further information on commonly used additives, such as
the additives discussed in Section 4.2.3, is discussed in Klamann,
"Lubricants and Related Products," Verlag Chemie, Deerfield Beach,
Fla. (ISBN 0-89573-177-0) and Ronney, M. W., "Lubricant Additives,"
Noyes Data Corporation, Parkridge, N.J. (1973). Additive packages
comprising one or more additives are commercially available for
blending with base stocks or a mixture of base stocks to formulate
lubricating oil compositions for meeting performance specifications
required for different applications or intended uses.
[0077] In certain embodiments, when lubricant oil composition
further comprises one or more additives, for example, one or more
additives discussed in Section 4.2.3, the additive(s) are blended
into the lubricant oil composition in an amount sufficient for the
additive(s) to perform the intended function. Exemplary amounts of
additives that may be blended with lubricant oil compositions
provided herein are shown in TABLE 2 below. In some embodiments,
the exemplary amount is the total for all additives of one type
comprised in the lubricant oil composition. For example, if the
lubricant oil composition comprises two or more detergents, the
total wt % of all detergents present in the lubricant oil
composition amounts to the wt % given in TABLE 2.
TABLE-US-00002 TABLE 2 Exemplary amounts Exemplary amounts Additive
in wt %.sup.# in wt %.sup.# Detergent(s) about 0.01-about 6.0 about
0.01-about 4.0 Dispersant(s) about 0.1-about 20 about 0.1-about 8
Antioxidant(s) about 0.01-about 5 about 0.01-about 1.5 Pour Point
about 0.01-about 5.0 about 0.01-about 1.5 Depressant(s) VI
Improver(s) about 0.01-about 0.25 about 0.01-about 0.25 Anti-Wear
and about 0.01-about 6 about 0.01-about 4 EP additive(s) Friction
Modifier(s) about 0.01-about 5 about 0.01-about 1.5 Demulsifier(s)
about 0.05-about 15 about 0.1-about 3 Antifoamant(s) about
0.001-about 3 about 0.001-about 0.15 Corrosion about 0.01-about 5
about 0.01-about 1.5 Inhibitor(s) Seal Swell about 0.01-about 3
about 0.01-about 2 Control Additive(s) Metal Deactivator(s) about
0.001-about 0.35 about 0.1-about 0.35 .sup.#wt % of total weight of
lubricant oil composition comprising one or more additives of the
same category.
[0078] In one embodiment, the lubricant oil composition consists
essentially of a first base oil component, a second base oil
component in the amount of about 0.1 wt % to about 90 wt %, and one
or more additives in the ranges listed in TABLE 2. In one
embodiment, the lubricant oil composition comprises a first base
oil component, a second base oil component in the amount of about
0.1 wt % to about 90 wt %, and one or more additives in the ranges
listed in TABLE 2. In another embodiment, the lubricant oil
composition comprises a first base oil component in the amount of
about 1 wt % to about 50 wt %, a second base oil component in the
amount of about 10 wt % to about 80 wt %, and one or more additives
in the ranges listed in TABLE 2.
[0079] Many of the commercially available additives are shipped
from the manufacturer and are provided with a certain amount of
base oil solvent. The wt % amounts in TABLE 2, as well as other
amounts mentioned in this disclosure, unless otherwise indicated
are directed to the amount of actual additive, i.e., the
non-solvent portion of the commercially available additive
mixture.
[0080] Additives and the amount in which they may be used for
lubricant oil compositions provided herein are, for example,
discussed in US2013/0090273, and WO 2004/031329 A2, each of which
is incorporated herein by reference in its entirety.
4.2.3.1 Detergents
[0081] In one embodiment, the lubricant oil composition provided
herein further comprises a detergent, or two or more detergents.
Such lubricant oil compositions further comprising a detergent, or
two or more detergents, can be used, for example, as internal
combustion engine oils.
[0082] Detergents are used in lubricating compositions. 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 acid, carboxylic acid, phosphorous acid, phenol, or
mixtures thereof. The counterion is typically an alkaline earth or
alkali metal.
[0083] Salts that contain a substantially stoichiometric amount of
the metal are described as neutral salts and have a total base
number ("TBN," as measured, for example, by ASTM D2896, 2011,
"Standard Test Method for Base Number of Petroleum Products by
Potentiometric Perchloric Acid Titration," ASTM International, West
Conshohocken, Pa., 2011, DOI: 10.1520/D2896-11, www.astm.org.) 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 (e.g., a metal hydroxide or oxide) with an acidic
gas (e.g., carbon dioxide). In one embodiment, the detergent is
neutral, mildly overbased, or highly overbased.
[0084] In one embodiment, the detergent is partly overbased.
Overbased detergents help neutralize acidic impurities produced by
the combustion process and become entrapped in the oil. In one
embodiment, the overbased detergent has a ratio of metallic ion to
anionic portion of the detergent of about 1.05:1 to about 50:1, or
from about 4:1 to about 25:1, on an equivalent basis. The resulting
detergent is an overbased detergent that will typically have a TBN
of about 150 or higher, often about 250 to 450 or more. In one
embodiment, the overbasing cation is sodium, calcium, or magnesium.
In one embodiment, the detergent is a mixture of detergents having
different TBNs.
[0085] In one embodiment, the detergent is an alkali or alkaline
earth metal salts of a sulfonates, phenate, carboxylate, phosphate,
or salicylate.
[0086] Sulfonates may be prepared from sulfonic acids that are
typically is obtained by sulfonation of alkyl substituted aromatic
hydrocarbons. Hydrocarbon examples include those obtained, for
example, by alkylating benzene, toluene, xylene, naphthalene,
biphenyl and their halogenated derivatives (chlorobenzene,
chlorotoluene, and chloronaphthalene, for example). The alkylating
agents typically have about 3 to 70 carbon atoms. The alkaryl
sulfonates typically contain about 9 to about 80 carbon or more
carbon atoms, more typically from about 16 to 60 carbon atoms.
[0087] Further, see Klamann, "Lubricants and Related Products,"
Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0) and C. V.
Smallheer and R. K. Smith "Lubricant Additives," Lezius-Hiles Co.
of Cleveland, Ohio (1967) for a description of overbased metal
salts of various sulfonic acids, which are useful as detergents in
the lubricant oil composition provided herein.
[0088] In another embodiment, the detergent is an alkaline earth
phenates. Alkaline earth phenates can be obtained by reacting
alkaline earth metal hydroxide or oxide (e.g., CaO, Ca(OH).sub.2,
BaO, Ba(OH).sub.2, MgO, Mg(OH).sub.2) with an alkyl phenol or
sulfurized alkylphenol. Such alkyl group includes straight chain or
branched (C.sub.1-C.sub.30) or (C.sub.4-C.sub.20) alkyl groups. The
phenol is, for example, isobutylphenol, 2-ethylhexylphenol,
nonylphenol, and dodecyl phenol. 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 (starting alkylphenols may contain more than one alkyl
substituent that are each independently straight chain or branched)
and sulfurizing agent (including elemental sulfur, sulfur halides,
such as sulfur dichloride) and then reacting the sulfurized phenol
with an alkaline earth metal base.
[0089] In another embodiment, the detergent is a metal salt of a
carboxylic acid. These carboxylic acid detergents may be prepared
by the reaction of 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.
In a particular embodiment, the detergent is a metal salt of
salicylic acid. In a certain embodiment, the salicylic acid is a
long chain alkyl salicylates. In a particular embodiment, the metal
salt of the salicylic acid is a compound of the following
formula:
##STR00005##
wherein R is a hydrogen atom or 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. In a certain embodiment, R is at least a C.sub.11, or
at least C.sub.13 alkyl chain. In a particular embodiment, R may be
optionally substituted with substituents that do not interfere with
the detergent's function. In one embodiment, M is calcium,
magnesium, or barium. In a particular embodiment, M is calcium. See
also US2013/0090273, which is incorporated herein by reference in
its entirety.
[0090] Hydrocarbyl-substituted salicylic acids may be prepared from
phenols by the Kolbe reaction. See U.S. Pat. No. 3,595,791 for
additional information on synthesis of these compounds, which is
incorporated herein by reference in its entirety. 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.
[0091] In one embodiment, the detergent is an alkaline earth metal
phosphates.
[0092] In one embodiment, the detergent is a simple detergent or a
hybrid or complex detergent. The hybrid or complex detergents can
provide the properties of two detergents without the need to blend
separate materials. See hereto U.S. Pat. No. 6,034,039, which is
incorporated herein by reference in its entirety.
[0093] In a particular embodiment, the detergent is a calcium
phenate, a calcium sulfonates, a calcium salicylates, a magnesium
phenates, a magnesium sulfonates, a magnesium salicylates, or
related components (such as borated detergents).
[0094] In one embodiment, the lubricant oil composition comprises a
detergent, two one or more detergents, in the amount of about 0.01
wt % to about 6.0 wt %, or about 0.1 wt % to about 4.0 wt % of the
total weight of the lubricant oil composition.
4.2.3.2 Dispersants
[0095] In one embodiment, the lubricant oil composition provided
herein further comprises a dispersant, or two or more dispersants.
Such lubricant oil compositions further comprising a dispersant, or
two or more dispersants, can be used, for example, as internal
combustion engine oils.
[0096] During engine operation, oil-insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposition on metal surfaces. In one
embodiment, the dispersant is ashless or ash-forming. In one
embodiment, 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.
[0097] In one embodiment, the dispersant is a high molecular weight
hydrocarbon chain, such as a hydrocarbon chain with 50 to 400
carbon atoms, with a polar group attached. In certain embodiments,
the polar group comprises at least one element of nitrogen, oxygen,
or phosphorus.
[0098] In certain embodiment, the dispersant is a phenate,
sulfonate, sulfurized phenate, salicylate, naphthenate, stearate,
carbamate, thiocarbamate, or phosphorus derivative. In a particular
embodiment, the dispersant is a alkenylsuccinic acid derivative,
produced by, for example, the reaction of a long chain substituted
alkenyl succinic compound, for example, a substituted succinic
anhydride, with a polyhydroxy or polyamino compound. The long chain
group constituting the oleophilic portion of the molecule, which
confers solubility in the oil, is, for example, a polyisobutylene
group. Exemplary U.S. patents describing dispersants are U.S. Pat.
Nos. 3,172,892; 3,2145,707; 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, all of which are incorporated herein by reference in
their entireties. Other dispersants 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; all of which are incorporated
herein by reference in their entireties. A further description of
dispersants may be found, for example, in European Patent
Application No. 471 071, which is incorporated herein by reference
in its entirety.
[0099] In one embodiment, the dispersant is a
hydrocarbyl-substituted succinic acid. In a particular embodiment,
the dispersant is a succinimide, succinate ester, or succinate
ester amide prepared by the reaction of a hydrocarbon-substituted
succinic acid compound having, for example, at least 50 carbon
atoms in the hydrocarbon substituent, with at least one equivalent
of an alkylene amine.
[0100] Succinimides are formed by the condensation reaction between
alkenyl succinic anhydrides and amines. Molar ratios can vary
depending on the polyamine. For example, the molar ratio of alkenyl
succinic anhydride to tetraethylenepentamine ("TEPA") can vary from
about 1:1 to about 5:1. Representative examples are disclosed 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 Pat. No. 1,094,044;
all of which are herein incorporated by reference in their
entireties.
[0101] Succinate esters are formed by the condensation reaction
between alkenyl succinic anhydrides and alcohols or polyols. Molar
ratios can vary depending on the alcohol or polyol used. In one
embodiment, the dispersant is obtained by the condensation of an
alkenyl succinic anhydride and pentaerythritol.
[0102] Succinate ester amides are formed by condensation reaction
between alkenyl succinic anhydrides and alkanol amines. In one
embodiment, the alkanol amines is ethoxylated polyalkylpolyamine,
propoxylated polyalkylpolyamine or a polyalkenylpolyamine, such as
polyethylene polyamine. In a particular embodiment, the alkanol
amine is propoxylated hexamethylenediamine. Representative examples
are shown in U.S. Pat. No. 4,426,305, which is herein incorporated
by reference in its entirety.
[0103] The molecular weight of the alkenyl succinic anhydrides used
in the preceding paragraphs is, for example, from about 800 to
about 2,500. The above products can be post-reacted with various
reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids
(e.g., oleic acid), and boron compounds (e.g., borate esters or
highly borated dispersants). The dispersants can be borated with
from about 0.1 to about 5 moles of boron per mole of dispersant
reaction product.
[0104] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See, for example, U.S. Pat.
No. 4,767,551, which is herein incorporated by reference in its
entirety. 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 about 800 to about 2,500.
Representative examples are disclosed 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; all of which are herein incorporated by reference in
their entirety.
[0105] Typical high molecular weight aliphatic acid modified
Mannich condensation products useful as dispersants for the
lubricant oil compositions provided herein can be prepared from
high molecular weight alkyl-substituted hydroxyaromatics or
HN(R).sub.2 group-containing reactants.
[0106] Examples of high molecular weight alkyl-substituted
hydroxyaromatic compounds can include polypropylphenol,
polybutylphenol, and other polyalkylphenols. These polyalkylphenols
can be obtained by the alkylation, in the presence of an alkylating
catalyst, such as BF.sub.3, of phenol with high molecular weight
polypropylene, polybutylene, and other polyalkylene compounds to
give alkyl substituents on the benzene ring of phenol having an
average 600-100,000 molecular weight.
[0107] Examples of HN(R).sub.2 group-containing reactants can
include alkylene polyamines, principally polyethylene polyamines.
Other representative organic compounds containing at least one
HN(R).sub.2 group suitable for use in the preparation of Mannich
condensation products include the mono- and di-amino alkanes and
their substituted analogs, e.g., ethylamine and diethanol amine;
aromatic diamines, e.g., phenylene diamine, diamino naphthalenes;
heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine,
imidazole, imidazolidine, and piperidine; melamine and their
substituted analogs.
[0108] Examples of alkylene polyamide reactants include
ethylenediamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentaamine, pentaethylene hexamine, hexaethylene
heptaamine, heptaethylene octaamine, octaethylene nonaamine,
nonaethylene decamine, and decaethylene undecamine and mixture of
such amines having nitrogen contents corresponding to the alkylene
polyamines, in the formula H.sub.2N--(Z--NH--).sub.nH, Z is a
divalent ethylene and n is 1 to 10 of the foregoing formula.
Corresponding propylene polyamines such as propylene diamine and
di-, tri-, tetra-, penta-propylene tri-, tetra-, penta- and
hexaamines are also suitable reactants. The alkylene polyamines are
usually obtained by the reaction of ammonia and dihalo alkanes,
such as dichloro alkanes. Thus the alkylene polyamines obtained
from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of
dichloroalkanes having 2 to 6 carbon atoms and the chlorines on
different carbons are suitable alkylene polyamine reactants.
[0109] Aldehyde reactants useful in the preparation of the high
molecular products useful in the preparation of the lubricant oil
compositions provided herein include the aliphatic aldehydes, such
as formaldehyde (also as paraformaldehyde and formalin),
acetaldehyde, and aldol (.beta.-hydroxybutyraldehyde). In certain
embodiments, formaldehyde or a formaldehyde-yielding reactant is
used.
[0110] Hydrocarbyl substituted amine ashless dispersant additives
are disclosed in, 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; all of which are
incorporated herein by reference in their entireties.
[0111] In certain embodiments, the dispersant can be a borated or
non-borated succinimide, for example, a derivatives from a
mono-succinimide, bis-succinimide, and/or mixture of mono- and
bis-succinimides, wherein the hydrocarbyl succinimide is derived
from a hydrocarbylene group such as polyisobutylene having a Mn
from about 500 to about 5000 or a mixture of such hydrocarbylene
groups. In another embodiment, the dispersant is a succinic
acid-ester or amide, alkylphenolpolyamine-coupled Mannich adduct,
its capped derivative (i.e., a blocked phenol), and other related
components.
[0112] Further, see Klamann, "Lubricants and Related Products,"
Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0) and C. V.
Smallheer and R. K. Smith "Lubricant Additives," Lezius-Hiles Co.
of Cleveland, Ohio (1967) for a description of overbased metal
salts of various sulfonic acids, which are useful as dispersants in
the lubricant oil composition provided herein.
[0113] In one embodiment, the lubricant oil composition comprises a
dispersant, or two or more dispersants in the amount of about 0.1
wt % to about 20 wt %, or about 0.1 wt % to about 8 wt % of the
total weight of the lubricant oil composition.
4.2.3.3 Antioxidants
[0114] In one embodiment, the lubricant oil composition provided
herein further comprises an antioxidant, or two or more
antioxidants. Such lubricant oil compositions further comprising an
antioxidant, or two or more antioxidants, can be used, for example,
as internal combustion engine oils.
[0115] 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 oil composition. A wide variety of antioxidants may be
used as additives for the lubricant oil compositions provided
herein. See, Klamann, "Lubricants and Related Products," Verlag
Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0), U.S. Pat. No.
4,798,684, and U.S. Pat. No. 5,084,197, for example, each of which
is incorporated herein by reference in its entirety.
[0116] In one embodiment, the antioxidant can be a phenol. In
certain embodiments, these phenolic anti-oxidants may be ashless
(metal-free) phenolic compounds or neutral or basic metal salts of
said phenol. Phenolic antioxidants for use in the lubricant oil
compositions provided herein are, for example, sterically hindered
phenols, which are phenols with a sterically hindered hydroxyl
group. A sterically hindered phenol, for example, includes those
derivatives of dihydroxy aryl compounds in which the hydroxyl
groups are in the o- or p-position to each other. In certain
embodiments, phenolic antioxidants include those sterically
hindered phenols substituted with alkyl groups of 6 or more carbon
atoms and the alkylene coupled derivatives of these hindered
phenols In a certain embodiment, the antioxidant is phenolic
antioxidant, such as 2-t-butyl-4-heptyl phenol, 2-t-butyl-4-octyl
phenol, 2-t-butyl-4-dodecyl phenol, 2,6-di-t-butyl-4-heptyl phenol,
2,6-di-t-butyl-4-dodecyl phenol, 2-methyl-6-t-butyl-4-heptyl
phenol, and 2-methyl-6-t-butyl-4-dodecyl phenol. In another
embodiment, the antioxidant are 2,6-di-alkyl-phenolic proprionic
ester derivatives. In a certain embodiment, the antioxidant is a
bis-phenolic antioxidant, such as and ortho-coupled phenols, for
example, 2,2'-bis(4-heptyl-6-t-butyl-phenol),
2,2'-bis(4-octyl-6-t-butyl-phenol), and
2,2'-bis(4-dodecyl-6-t-butyl-phenol), or such as para-coupled
bisphenols, for example, 4,4'-bis(2,6-di-t-butyl phenol) and
4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0117] In one embodiment, the antioxidant can be a non-phenolic
antioxidant, for example, an aromatic amine antioxidants. In a
certain embodiment, the lubricant oil composition comprises at
least a first and a second additive, wherein the first additive is
a non-phenolic antioxidant and the second additive is a phenolic
antioxidant. In a certain embodiment, the non-phenolic antioxidant
is, for example, an alkylated and non-alkylated aromatic amines,
such as aromatic monoamines of Formula R.sup.8R.sup.9R.sup.10N,
wherein 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 R.sup.8 is an aliphatic, aryl, or heteroaryl,
wherein the aryl groups is optionally substituted or substituted
aromatic group, R.sup.9 is an aromatic or a substituted aromatic
group, and R.sup.10 is H, alkyl, aryl (wherein the substituents are
defined as in WO2004/031329A2, which is incorporated herein by
reference in its entirety); and R.sup.11S(O).sub.XR.sup.12, wherein
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 (wherein the substituents are defined as in
WO2004/031329A2). Furthermore, the aliphatic group R.sup.8 may
contain from 1 to about 20 carbon atoms, or contains from about 6
to 12 carbon atoms. The aliphatic group is a saturated aliphatic
group. In one embodiment, 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.
[0118] In a particular embodiment, the aromatic amine antioxidant
has a (C.sub.6-C.sub.14) alkyl substituent. The alkyl is, for
example, hexyl, heptyl, octyl, nonyl, and decyl. In certain
embodiment, the aromatic amine antioxidant is, for example,
diphenylamine, phenyl naphthylamine, phenothiazine, imidodibenzyl,
and diphenyl phenylene diamine. In a particular embodiment, the
aromatic amine antioxidant is, for example,
p,p'-dioctyldiphenylamine; t-octylphenyl-alphanaphthylamine;
phenyl-alpha naphthylamine; and p-octylphenyl-alphanaphthylamine.
In some embodiments, the lubricant oil composition provided herein
contains two or more aromatic amine antioxidants. In one
embodiment, the antioxidant is a polymeric amine antioxidant.
[0119] In one embodiment, the antioxidant is a sulfurized alkyl
phenols, or alkali or alkaline earth metal salts thereof.
[0120] In one embodiment, the antioxidant is a copper compound. In
a certain embodiment, the copper compound is an oil-soluble copper
compound. In a particular embodiment, the copper compound is, for
example, copper dihydrocarbyl thio- or dithiophosphates, copper
salts of carboxylic acids (naturally occurring or synthetic),
copper dithiacarbamates, copper sulphonates, copper phenates, and
copper acetylacetonates. In a certain embodiment, the copper
compound is a basic, neutral, or acidic copper Cu(I) or Cu(II)
salt, derived from alkenyl succinic acids or anhydrides.
[0121] In a particular embodiment, an antioxidant is a sterically
hindered phenol or an arylamine. In a certain embodiment, the
antioxidant provided herein may be used individually or in
combination with one another.
[0122] In one embodiment, the lubricant oil composition comprises
an antioxidant, or two or more antioxidants, in the amount of about
0.01 wt % to about 5 wt %, about 0.01 wt % to about 1.5 wt %, or
less than about 1.5 wt %, of the total weight of the lubricant oil
composition. In a particular embodiment, the lubricant oil
composition does not comprise an antioxidant.
4.2.3.4 Pour Point Depressants
[0123] In one embodiment, the lubricant oil composition provided
herein further comprises a pour point depressant, or two or more
pour point depressants. Such lubricant oil compositions further
comprising a pour point depressant, or two or more pour point
depressants, can be used, for example, as internal combustion
engine oils.
[0124] Conventional pour point depressants (also known as lube oil
flow improvers) may be added to the lubricant oil compositions
provided herein. These pour point depressant may be added to the
lubricating oil composition provided herein to, for example, lower
the minimum temperature at which the fluid will flow or can be
poured. In one embodiment, the pour point depressant is a
polymethacrylate, a polyacrylate, a polyarylamide, a condensation
product of haloparaffin waxes and aromatic compounds, a vinyl
carboxylate polymer, or terpolymer of dialkylfumarates, a vinyl
ester of a fatty acid and an allyl vinyl ether. For further
description of pour point depressant and/or the preparation of the
same, see 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; all of which are incorporated herein by reference in
their entireties.
[0125] In one embodiment, the lubricant oil composition comprises a
pour point depressant, or two or more pour point depressants, in
the amount of about 0.01 wt % to about 5 wt %, or about 0.01 wt %
to about 1.5 wt %, of the total weight of the lubricant oil
composition.
4.2.3.5 VI Improvers
[0126] In one embodiment, the lubricant oil composition provided
herein further comprises a VI improver, or two or more VI
improvers. Such lubricant oil compositions further comprising a VI
improver, or two or more VI improvers, can be used, for example, as
internal combustion engine oils.
[0127] In one embodiment, VI improvers include high molecular
weight hydrocarbons, polyesters and VI improver dispersants that
function as both a viscosity index improver and a dispersant. In a
certain embodiment, the molecular weight of these VI improver
polymers is between about 1,000 Da to about 1,000,000 Da, or about
25,000 Da to about 500,000 Da, or about 50,000 Da to about 400,000
Da. In another embodiment, the VI improvers have a shear stability
index (SSI) of, for example, about 4 to about 65. Examples of VI
improvers are polymers and copolymers of methacrylate, butadiene,
olefins, or alkylated styrenes. Polyisobutylene is a VI improver.
In one embodiment, VI improvers are polymethacrylates (for example,
copolymers of various chain length alkyl methacrylates) and
polyacrylates (for example, copolymers of various chain length
acrylates).
[0128] In another embodiment, VI improvers are copolymers of
ethylene and propylene or copolymers of propylene and butylene. In
certain embodiments, these copolymers have a molecular weight of
about 100,000 Da to about 400,000 Da. In certain embodiments,
hydrogenated block copolymers of styrene and isoprene can be used.
In a particular embodiment, the copolymer is a styrene-isoprene or
styrene-butadiene based polymer having a molecular weight of about
50,000 Da to about 200,000 Da.
[0129] In one embodiment, the lubricant oil composition comprises a
VI improver, or two or more VI improvers, in the amount of about
0.01 wt % to about 0.25 wt %, of the total weight of the lubricant
oil composition.
4.2.3.6 Anti-Wear Agents or Extreme Pressure Additives
[0130] In one embodiment, the lubricant oil composition provided
herein further comprises an anti-wear agent, or two or more
anti-wear agents. Such lubricant oil compositions further
comprising an anti-wear agent, or two or more anti-wear agents, can
be used, for example, as internal combustion engine oils. In one
embodiment, the lubricant oil composition provided herein further
comprises an extreme pressure additive, or two or more extreme
pressure additives. Such lubricant oil compositions further
comprising an extreme pressure additive, or two or more extreme
pressure additives, can be used, for example, as internal
combustion engine oils.
[0131] The anti-wear or extreme pressure ("EP") additives provide,
for example, adequate anti-wear protection for the combustion
engine. Anti-wear or extreme EP additives inter alia reduce
friction and wear of engine metal parts.
[0132] In one embodiment, the anti-wear additive for use in, for
example, internal combustion engine crankcase oils, is a metal
alkylthiophosphate, in particular a metal dialkyldithiophosphate,
in which the primary metal constituent is zinc, or zinc
dialkyldithiophosphate ("ZDDP"). In certain embodiments, ZDDP
compounds are compounds of Formula III.
Zn[SP(S)(OR.sup.1)(OR.sup.2)].sub.2 Formula III
wherein R.sup.1 and R.sup.2 are (C.sub.1-C.sub.18)alkyl groups. In
a particular embodiment, R.sup.1 and R.sup.2 are
(C.sub.2-C.sub.12)alkyl groups.
[0133] In one embodiment, the anti-wear additive is a
phosphorus-free anti-wear additive. In certain embodiments, the
anti-wear additives in the lubricant oil composition further
comprise two or more anti-wear additives, wherein a first anti-wear
additive is ZDDP and a second anti-wear additive is a
phosphorus-free anti-wear additive.
[0134] In certain embodiments, the anti-wear additive is a
sulfurized olefin. Sulfurized olefins can be prepared, for example,
by sulfurization or various organic materials, such as aliphatic,
arylaliphatic, alicyclic olefinic hydrocarbons containing, for
example, from 3 to 30 carbon atoms or 3 to 20 carbon atoms (see
Leslie R. Rudnick Lubricant Additives: Chemistry and Applications
(Second Edition) and references cited therein).
[0135] In certain embodiments, the EP additive is a sulfurized
olefin.
[0136] The sulfurized olefins provided herein are olefins of
Formula IV
R.sup.3R.sup.4C.dbd.CR.sup.5R.sup.6 Formula IV
wherein each of R.sup.3-R.sup.6 independently is hydrogen, alkenyl,
or alkenyl. Any two of R.sup.3-R.sup.6 may be connected so as to
form a cyclic ring. Additional information concerning sulfurized
olefins and their preparation can be found in U.S. Pat. No.
4,941,984, incorporated herein in its entirety.
[0137] In certain embodiments, the anti-wear agent is a
thiocarbamate/molybdenum complex, such as moly-sulfur
(C.sub.8-C.sub.18)alkyl dithiocarbamate trimer complex.
[0138] In certain embodiments, the anti-wear agent is an ester of
glycerol, such as mono-, di-, and tri-oleates, mono-palmitates and
mono-myristates.
[0139] Further anti-wear agents or EP additives are disclosed in
U.S. Pat. No. 2,443,264, U.S. Pat. No. 2,471,115, U.S. Pat. No.
2,526,497, and U.S. Pat. No. 2,591,577 (polysulfides of
thiophosphorus acids and thiophosphorus acid esters as additives);
U.S. Pat. No. 3,770,854 (phosphorothionyl disulfides); U.S. Pat.
No. 4,501,678 (alkylthiocarbamoyl compounds (e.g.,
bis(dibutyl)thiocarbamoyl) in combination with a molybdenum
compound (e.g., oxymolybdenum diisopropyl-phosphorodithioate
sulfide) and a phosphorous ester (e.g., dibutyl hydrogen
phosphite)); U.S. Pat. No. 4,758,362 (carbamate additives); U.S.
Pat. No. 5,693,598 (thiocarbamate); U.S. Pat. No. 5,034,141
(combination of a thiodixanthogen compound (e.g.,
octylthiodixanthogen) and a metal thiophosphate (e.g., ZDDP)); can
improve anti-wear properties, each of which is incorporated herein
by reference in its entirety.
[0140] In certain embodiments, the anti-wear agent is a phosphorus
and sulfur compound, such as zinc dithiophosphate and/or sulfur,
nitrogen, boron, molybdenum phosphorodithioates, molybdenum
dithiocarbamates and various organo-molybdenum derivatives, such as
heterocyclic compounds, for example, dimercaptothiadiazoles,
mercaptobenzothiadiazoles, and triazines. In a particular
embodiment, the anti-wear agent is an alicyclic, an amine, an
alcohol, an ester, a diol, a triol, a fatty amide and the like can
also be used.
[0141] In one embodiment, the lubricant oil composition comprises
an anti-wear agent, or two or more anti-wear agents, in the amount
of about 0.01 wt % to about 6 wt %, or about 0.01 wt % to about 4
wt %, of the total weight of the lubricant oil composition. In
another embodiment, the lubricant oil composition comprises an EP
additive, or two or more EP additives, in the amount of about 0.01
wt % to about 6 wt %, or about 0.01 wt % to about 4 wt %, of the
total weight of the lubricant oil composition.
4.2.3.7 Friction Modifiers
[0142] In one embodiment, the lubricant oil composition provided
herein further comprises a friction modifier, or two or more
friction modifiers. Such lubricant oil compositions further
comprising a friction modifier, or two or more friction modifiers,
can be used, for example, as internal combustion engine oils.
[0143] 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 oil
compositions provided herein.
[0144] Friction modifiers may include metal-containing compounds or
materials as well as ashless compounds or materials, or mixtures
thereof. Metal-containing friction modifiers may include metal
salts or metal-ligand complexes where the metals may include
alkali, alkaline earth, or transition group metals. Such
metal-containing friction modifiers may also have low-ash
characteristics. Transition metals may include Mo, W, Sb, Sn, Fe,
Cu, Zn, and others. Ligands may include hydrocarbyl derivative of
alcohols, polyols, glycerols, partial ester glycerols, thiols,
carboxylates, carbamates, thiocarbamates, dithiocarbamates,
phosphates, thiophosphates, dithiophosphates, amides, imides,
amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles,
and other polar molecular functional groups containing effective
amounts of O, N, S, or P, individually or in combination. In
particular, Mo-containing compounds can be particularly effective
such as for example Mo-dithiocarbamates, Mo(DTC),
Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo(Am), Mo-alcoholates,
Mo-alcohol-amides, and the like. See U.S. Pat. Nos. 5,824,627;
6,232,276; 6,153,564; 6,143,701; 6,110,878; 5,837,657; 6,010,987;
5,906,968; 6,734,150; 6,730,638; 6,689,725; 6,569,820; WO99/66013;
WO99/47629; and WO98/26030; all of which are incorporated herein by
reference in their entireties. Also in particular W-containing
compounds can be particularly effective, such as for example amine
tungstates described in U.S. Pat. Nos. 3,290,245; 7,820,602;
8,030,256; 8,080,500; 8,080,500; 7,858,565; 7,879,777; all of which
are incorporated herein by reference in their entireties.
[0145] Ashless friction modifiers may have also include lubricant
materials that contain effective amounts of polar groups, for
example, hydroxyl-containing hydrocarbyl base oils, glycerides,
partial glycerides, glyceride derivatives, and the like. Polar
groups in friction modifiers may include hydrocarbyl groups
containing effective amounts of O, N, S, or P, individually or in
combination. Other friction modifiers that may be particularly
effective include, for example, salts (both ash-containing and
ashless derivatives) of fatty acids, fatty alcohols, fatty amides,
fatty esters, hydroxyl-containing carboxylates, and comparable
synthetic long-chain hydrocarbyl acids, alcohols, amides, esters,
hydroxylcarboxylates, and the like. In some instances fatty organic
acids, fatty amines, and sulfurized fatty acids may be used as
suitable friction modifiers.
[0146] Concentrations of molybdenum-containing materials are often
described in terms of Mo metal concentration. Advantageous
concentrations of Mo may range from about 10 ppm to about 3000 ppm
or more, from about 20 to about 2000 ppm, or from about 30 to about
1000 ppm. Friction modifiers of all types may be used alone or in
mixtures with lubricant oil composition provided herein. In one
embodiment, the lubricant oil composition comprises mixtures of two
or more friction modifiers, or mixtures of friction modifier(s)
with alternate surface active material(s).
[0147] In one embodiment, the lubricant oil composition comprises a
friction modifier, or two or more friction modifiers, in the amount
of about 0.01 wt % to about 10-15 wt %, or about 0.1 wt % to about
5 wt %, of the total weight of the lubricant oil composition. In
another embodiment, the lubricant oil composition comprises a
friction modifier, or two or more friction modifiers, in the amount
of about 0.01 wt % to about 5 wt %, or about 0.1 wt % to about 1.5
wt %, of the total weight of the lubricant oil composition.
4.2.3.8 Demulsifiers
[0148] In one embodiment, the lubricant oil composition provided
herein further comprises a demulsifier, or two or more
demulsifiers. Such lubricant oil compositions further comprising a
demulsifier, or two or more demulsifiers, can be used, for example,
as internal combustion engine oils.
[0149] Demulsifying agents are, for example, alkoxylated phenols
and phenol-formaldehyde resins and synthetic alkylaryl sulfonates,
such as metallic dinonylnaphthalene sulfonates. In one embodiment,
the demulsifing agent is a polymer comprising a polyoxyalkylene
glycol having a molecular weight of about 450 Da to about 5000 Da,
or more than 5000 Da. In another embodiment, a demulsifier
comprises a polyoxyalkylene glycol produced from alkoxylation of
n-butanol with a mixture of alkylene oxides to form a random
alkoxylated product. In a particular embodiment, the demulsifier
comprises a polyoxyalkylene glycol produced by alkoxylation of
n-butanol with a mixture of alkylene oxides to form a random
alkoxylated product.
[0150] In one embodiment, the lubricant oil composition comprises a
demulsifier, or two or more demulsifiers, in the amount of about
0.05 wt % to about 15 wt %, or about 0.1 wt % to about 3 wt %, of
the total weight of the lubricant oil composition.
4.2.3.9 Antifoamants
[0151] In one embodiment, the lubricant oil composition provided
herein further comprises an antifoamant, or two or more
antifoamants. Such lubricant oil compositions further comprising an
antifoamant, or two or more antifoamants, can be used, for example,
as internal combustion engine oils.
[0152] Antifoamants may be added to lubricant oil compositions
provided herein. These agents retard the formation of stable foams.
In one embodiment, the antifoamant is a silicone or organic
polymer. In a particular embodiment, the antifoamant is a
polysiloxane, such as silicon oil or polydimethyl siloxane.
[0153] In one embodiment, the lubricant oil composition comprises
an antifoamant, or two or more antifoamants, in the amount of about
less than about 1 wt %, or less than about 0.1 wt %. In another
embodiment, the lubricant oil composition comprises an antifoamant,
or two or more antifoamants, in the amount of about less than about
0.001 wt %, to about 3 wt %, or about 0.001 wt % to about 0.15 wt
%, of the total weight of the lubricant oil composition.
4.2.3.10 Corrosion Inhibitors
[0154] In one embodiment, the lubricant oil composition provided
herein further comprises a corrosion inhibitor, or two or more
corrosion inhibitors. Such lubricant oil compositions further
comprising a corrosion inhibitor, or two or more corrosion
inhibitors, can be used, for example, as internal combustion engine
oils.
[0155] Corrosion inhibitors are used to reduce the degradation of
metallic parts that are in contact with the lubricating oil
composition. Suitable corrosion inhibitors include thiadiazoles.
See, for example, U.S. Pat. Nos. 2,719,125; 2,719,126; and
3,087,932, all of which are incorporated herein by reference in
their entireties.
[0156] Corrosion inhibitors further protect lubricated metal
surfaces against chemical attack by water or other contaminants. A
wide variety of corrosion inhibitors are commercially available;
they are referred to in Klamann, "Lubricants and Related Products,"
Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0). One type
of corrosion inhibitor is a polar compound that wets the metal
surface, protecting it with a film of oil. Another type of
corrosion inhibitor absorbs water by incorporating it in a
water-in-oil emulsion, so that only the oil touches the metal
surface. Yet another type of corrosion inhibitor chemically adheres
to the metal to produce a non-reactive surface. In one embodiment,
the corrosion inhibitor is a zinc dithiophosphate, a metal
phenolate, a basic metal sulfonate, a fatty acids, or an amine.
[0157] In one embodiment, the lubricant oil composition comprises a
corrosion inhibitor, or two or more corrosion inhibitors, in the
amount of about 0.01 wt % to about 5 wt %, or about 0.01 wt % to
about 1.5 wt %, of the total weight of the lubricant oil
composition.
4.2.3.11 Seal Swell Control Additives
[0158] In one embodiment, the lubricant oil composition provided
herein further comprises a seal swell control additive, or two or
more seal swell control additives. Such lubricant oil compositions
further comprising a seal swell control additive, or two or more
seal swell control additives, can be used, for example, as internal
combustion engine oils.
[0159] 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
are, for example, organic phosphates, aromatic esters, aromatic
hydrocarbons, esters (e.g., butylbenzyl phthalate), and polybutenyl
succinic anhydride.
[0160] In one embodiment, the lubricant oil composition comprises a
seal swell control additive, or two or more seal swell control
additives, in the amount of about 0.01 wt % to about 3 wt %, or
about 0.01 wt % to about 2 wt %, of the total weight of the
lubricant oil composition.
4.2.3.12 Metal Deactivators
[0161] In one embodiment, the lubricant oil composition provided
herein further comprises a metal deactivator, or two or more metal
deactivators. Such lubricant oil compositions further comprising a
metal deactivator, or two or more metal deactivators, can be used,
for example, as internal combustion engine oils.
[0162] In one embodiment, a metal deactivator is a
2,5-dimercapto-1,3,4-thiadiazole or a derivative thereof, a
mercaptobenzothiazole, an alkyltriazole, or a benzotriazole. In one
embodiment, the metal deactivator is a diacid, such as sebacic
acid, adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic
acid, 3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and
fumaric acid.
[0163] In another embodiment, the metal deactivator is a straight
or branch-chained, saturated or unsaturated monocarboxylic acid or
ester thereof, which may optionally be sulphurized in an amount up
to 35% by weight. In one embodiment, the acid is a C.sub.4 to
C.sub.22 straight chain unsaturated monocarboxylic acid. In a
particular embodiment, the metal deactivator is a monocarboxylic
acid, such as sulphurised oleic acid. In another embodiment, the
metal deactivator is oleic acid, valeric acid, or erucic acid. In a
certain embodiment, the metal deactivator is a triazole. In a
particular embodiment, the triazole is a tolylotriazole. In another
embodiment, the metal deactivator is a thiazole and certain diamine
compounds known to the person of ordinary skill in the art. In one
embodiment, the metal deactivator is a triazole, benzotriazole or
substituted benzotriazole, such as an alkyl substituted
benzotriazoles. The alkyl substituent generally contains up to up
to 8 carbon atoms. The triazoles may be optionally substituted
with, for example, halogen, nitro, amino, and mercapto. In certain
embodiments, the metal deactivator is a triazole, wherein the
triazole is benzotriazole, tolyltriazole, ethylbenzotriazole,
hexylbenzotriazole, octylbenzotriazole, chlorobenzotriazole, or
nitrobenzotriazole. In a particular embodiment, the metal
deactivator is benzotriazole or tolyltriazole. In one embodiment,
the metal deactivator is a straight or branched chain saturated or
unsaturated monocarboxylic acid which is optionally sulphurised in
an amount which may be up to 35% by weight, or an ester of such an
acid; a triazole or alkyl derivatives thereof; or a triazole
selected from 1,2,4 triazole, 1,2,3 triazole,
5-anilo-1,2,3,4-thiatriazole, 3-amino-1,2,4 triazole,
1-H-benzotriazole-1-yl-methylisocyanide,
methylene-bis-benzotriazole and naphthotriazole.
[0164] In one embodiment, the lubricant oil composition comprises a
metal deactivator, or two or more metal deactivators, in the amount
of about 0.001 wt % to about 0.35 wt %, or about 0.1 wt % to about
0.35 wt % of the total weight of the lubricant oil composition.
4.3 Methods and Formulation
[0165] Provided herein is a method of improving oxidation
resistance, swell characteristics, deposit performance, reserve
alkalinity, rust preventing quality, or levels of ash-forming
compounds of a lubricating oil composition described herein by
mixing a first base oil component provided herein with a second
base oil component provided herein and optionally one or more
additives, wherein said oxidation resistance, swell
characteristics, deposit performance, reserve alkalinity, rust
preventing quality, or levels of ash-forming compound of a
lubricating oil composition are improved as compared to an oil
composition comprising the second base oil component as provided
herein, but not comprising the first base oil component as provided
herein.
[0166] Further provided herein is a method of improving fuel
efficiency in an internal combustion engine by lubricating said
engine with a lubricant oil composition provided herein, wherein
the fuel efficiency is improved as compared to fuel efficiency
achieved by lubricating said engine with an oil composition
comprising the second base oil component as provided herein, but
not comprising the first base oil component as provided herein.
[0167] A lubricant oil composition can be made using the first base
oil component by blending or admixing the second base oil
component, an optional additive package comprising an effective
amount of at least one additive, such as a detergent, a dispersant,
an antioxidant, a pour point depressant, a VI improver, an
anti-wear agent, an extreme pressure additive, a friction modifier,
a demulsifier, an antifoamanta corrosion inhibitor, a seal swell
control additive, or a metal deactivator. An effective amount of
one or more additives, or an additive package containing one or
more such additives, is added to, blended into or admixed with the
base stock to meet one or more formulated product specifications,
such as those relating to a lube oil for diesel engines, internal
combustion engines, automatic transmissions, turbine or jet,
hydraulic oil, industrial oil, etc., as is known. 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; and "Lubricant Additives" by M. W. Ronney, published
by Noyes Data Corporation, Parkridge, N.J. (1973). Additive
packages for adding to a base stock or to a blend of base stocks to
form fully formulated lubricated oil compositions for meeting
performance specifications required for different applications or
intended uses are commercially available.
[0168] In particular, the lubricant oil compositions provided
herein can be prepared using conventional techniques. For example,
Group II and/or Group III base oils and alkylated naphthalene can
be added to a reaction vessel and mixed at temperatures from about
40.degree. C. to about 60.degree. C. for a period of time ranging
from about 20 minutes to about 2 hours.
[0169] The following examples are presented to illustrate the
lubricant oil compositions provided herein and should not be
construed to limit the claimed invention.
5 EXAMPLES
5.1 Example 1
Preparation of Monoalkyl Naphthalenes
[0170] The monoalkyl naphthalenes of the current invention can be
made in any of the ways known to those skilled in the art. For
example, alpha olefins and Guerbet alcohols were used as
electrophiles in reactions with naphthalene in the presence of
suitable catalysts to prepare the monoalkyl naphthalene used in the
practice of the present invention.
[0171] Specifically, Alkylate 32 was prepared by the alkylation of
naphthalene with Guebert alcohol Isofol 18E (mixture of 3.0 wt
%-6.0 wt % of 2-hexyldecanol, 85.0 wt % to 90.0 wt % of
2-octyldecanol and 2-hexyldodecanol, and 3.0 wt % to 6.0 wt % of
2-octyldodecanol) using a rare earth triflate salt, such as
Sc(OTf).sub.3, as a catalyst by methods known to those skilled in
the art.
[0172] Similarly, Alkylate 30 was prepared by the alkylation of
naphthalene with a mixture of alpha olefins of chain length of 18
to 26 carbon atoms, using standard Friedel-Crafts alkylation
methods known to those skilled in the art.
5.2 Example 2
[0173] This Example presents Kinematic Viscosity, Viscosity Index
and Noack Volatility data for exemplary compounds of Formula (I)
and for Synesstic.TM. 5 (ExxonMobil Chemical Company, 13501 Katy
Freeway, Houston, Tex. 77079-1398, USA), an exemplary state of the
art commercially available alkylated naphthalene.
[0174] For Alkylate 30 and Alkylate 32, prepared as described in
Example 1, as well as, commercially available Synesstic.TM. 5 the
parameters shown in TABLE 3 were determined.
TABLE-US-00003 TABLE 3 Synesstic Alkylate Alkylate Properties 5 30
32 Kinematic Viscosity at 100.degree. C. 4.7 5.7 6.8 (ASTM D445,
cSt) Kinematic Viscosity at 40.degree. C. 29.0 38.7 46.4 (ASTM
D445, cSt) Viscosity Index 77 80 100 (ASTM D2270) Noack Volatility
12.7 7.1 3.7 (ASTM D5800, % lost) 250.degree. C.
[0175] The data presented in TABLE 3, TABLE 5, TABLE 7, and TABLE 9
has been obtained using the following standardized methods: [0176]
ASTM Standard ASTM D445, 2012, "Standard Test Method for Kinematic
Viscosity of Transparent and Opaque Liquids (and Calculation of
Dynamic Viscosity)," ASTM International, West Conshohocken, Pa.,
2012, DOI: 10.1520/D0445-12, www.astm.org; [0177] ASTM D2270,
2010e1, "Standard Practice for Calculating Viscosity Index From
Kinematic Viscosity at 40 and 100.degree. C.," ASTM International,
West Conshohocken, Pa., 2010, DOI: 10.1520/D2270-10E01,
www.astm.org; and [0178] ASTM D5800, 2010, "Standard Test Method
for Evaporation Loss of Lubricating Oils by the Noack Method," ASTM
International, West Conshohocken, Pa., 2010, DOI: 10.1520/D5800-10,
www.astm.org.
[0179] This Example demonstrates that the exemplary compounds
Formula (I) presented in this Example have a higher Viscosity Index
and lower Noack Volatility compared to Synesstic.TM. 5, an
exemplary state of the art commercially available alkylated
naphthalene.
5.3 Example 3
[0180] This Example presents Kinematic Viscosity, Viscosity Index
and Noack Volatility data for exemplary lubricant oil compositions
as provided herein.
[0181] Alkylate 30, prepared as described in Example 1, was blended
with low viscosity PAOs (Synfluid.RTM. PAOs available from Chevron
Phillips Chemical (Synfluid.RTM. PAO 4 cSt, and Synfluid.RTM. PAO 5
cSt available from Chevron Phillips Chemical Company LLC, 10001 Six
Pines Drive, The Woodlands, Tex. 77380), in the proportions
described in TABLE 4.
TABLE-US-00004 TABLE 4 Lubricant Oil Composition Ingredients A B C
D Alkylate 30 20 20 30 30 (wt % of total weight) 4.0 cSt PAO
(Synfluid .RTM. PAO 4 cSt) 40 50 30 50 (wt % of total weight) 5.0
cSt PAO (Synfluid .RTM. PAO 5 cSt) 40 30 40 20 (wt % of total
weight)
[0182] TABLE 5 shows the measured properties of Lubricant Oil
Compositions A-D.
TABLE-US-00005 TABLE 5 Lubricant Oil Composition Properties A B C D
Kinematic Viscosity at 100.degree. C. 4.7 4.6 4.9 4.6 (ASTM D445,
cSt) Kinematic Viscosity at 40.degree. C. 22.9 22.0 24.9 23.1 (ASTM
D445, cSt) Viscosity Index 126 127 122 115 (ASTM D2270) Noack
Volatility 9.2 9.9 8.6 9.9 (ASTM D5800, % lost) 250.degree. C.
5.4 Example 4
[0183] This Example presents Kinematic Viscosity, Viscosity Index
and Noack Volatility data for exemplary lubricant oil compositions
provided herein.
[0184] Alkylate 32, prepared as described in Example 1, was blended
with low viscosity PAOs (Synfluid.RTM. PAOs available from Chevron
Phillips Chemical (Synfluid.RTM. PAO 4 cSt, and Synfluid.RTM. PAO 5
cSt available from Chevron Phillips Chemical Company LLC, 10001 Six
Pines Drive, The Woodlands, Tex. 77380), in the proportions
described in TABLE 6
TABLE-US-00006 TABLE 6 Lubricant Oil Composition Ingredients E F G
H Alkylate 32 20 20 30 30 (wt % of total weight) 4.0 cSt
PAO(Synfluid .RTM. PAO 4 cSt) 40 50 30 50 (wt % of total weight)
5.0 cSt PAO(Synfluid .RTM. PAO 5 cSt) 40 30 40 20 (wt % of total
weight)
[0185] TABLE 7 shows the measured properties of the Lubricant Oil
Compositions E-F.
TABLE-US-00007 TABLE 7 Lubricant Oil Composition Properties E F G H
Kinematic Viscosity at 100.degree. C. 4.9 4.7 5.2 4.9 (ASTM D445,
cSt) Kinematic Viscosity at 40.degree. C. 23.7 22.9 26.3 24.4 (ASTM
D445, cSt) Viscosity Index 134 126 132 127 (ASTM D2270) Noack
Volatility 8.5 9.2 7.6 8.9 (ASTM D5800, % lost) 250.degree. C.
5.5 Example 5
[0186] This Example presents Kinematic Viscosity, Viscosity Index
and Noack Volatility data for comparative lubricant oil
compositions comprising Synesstic.TM. 5 (ExxonMobil Chemical
Company, 13501 Katy Freeway, Houston, Tex. 77079-1398, USA), an
exemplary state of the art commercially available alkylated
naphthalene.
[0187] Synesstic.TM. 5 was blended with low viscosity PAOs
(Synfluid.RTM. PAOs available from Chevron Phillips Chemical
(Synfluid.RTM. PAO 4 cSt, and Synfluid.RTM. PAO 5 cSt available
from Chevron Phillips Chemical Company LLC, 10001 Six Pines Drive,
The Woodlands, Tex. 77380), in the proportions described in TABLE
8.
TABLE-US-00008 TABLE 8 Comparative Lubricant Oil Composition
Ingredients I II III IV Synesstic .TM. 5 20 20 30 30 (wt % of total
weight) 4.0 cSt PAO(Synfluid .RTM. PAO 4 cSt) 40 50 30 50 (wt % of
total weight) 5.0 cSt PAO(Synfluid .RTM. PAO 5 cSt) 40 30 40 20 (wt
% of total weight)
[0188] TABLE 9 shows the measured properties of the Comparative
Lubricant Oil Compositions I-IV.
TABLE-US-00009 TABLE 9 Comparative Lubricant Oil Composition
Properties I II III IV Kinematic Viscosity at 100.degree. C. 4.6
4.4 4.7 4.3 (ASTM D445, cSt) Kinematic Viscosity at 40.degree. C.
21.6 20.8 22.9 21.2 (ASTM D445, cSt) Viscosity Index 132 123 126
109 (ASTM D2270) Noack Volatility 10.3 11.0 10.3 11.6 (ASTM D5800,
% lost) 250.degree. C.
[0189] The Example demonstrates that the Lubricant Oil Compositions
A-H relative to the Comparative Lubricant Oil Compositions I-IV
have lower Noack Volatility, while maintaining low Kinematic
Viscosity.
5.6 Example 6
[0190] The methods provided in this example are used to demonstrate
oxidation resistance, swell characteristics, deposit performance,
reserve alkalinity, rust preventing qualities, and levels of
ash-forming compounds of lubricant oil compositions provided
herein.
[0191] The lubricant oil compositions demonstrates CCS viscosities
at -35.degree. C., as determined by ASTM D5293, of less than 6200
mPas, less than 5000 mPas, less than 4000 mPas, less than 3500
mPas, less than 3000 mPas, less than 2500 mPas, less than 2000
mPas, or less than 1700 mPas.
[0192] The lubricant oil compositions demonstrates
high-temperature, high-shear (HTHS) viscosities at 150.degree. C.,
as determined by ASTM D4683 of less than 2.6 mPas, less than 2.3
mPas, less than 2.0 mPas, or less than 1.85 mPas.
[0193] Oxidation Resistance
[0194] The oxidation resistance of lubricant oil compositions is
determined using ASTM D4310, 2010, "Standard Test Method for
Determination of Sludging and Corrosion Tendencies of Inhibited
Mineral Oils," ASTM International, West Conshohocken, Pa., 2010,
DOI: 10.1520/D4310-10, www.astm.org. Oxidation resistance is the
ability of oil to resist the direct and indirect attack of oxygen
during engine operation. This test method is used to evaluate the
tendency of oils to corrode copper catalyst metal and to form
sludge during oxidation in the presence of oxygen, water, and
copper and iron metals at an elevated temperature. The way in which
oil is formulated determines its ability to resist oxidation. The
oxidation stability (oxidation lifetime) is determined by following
the acid number of lubricant oil composition for a certain number
of test hours required for the oil to reach an acid number of 2.0
mg KOH/g.
[0195] Swell Characteristics
[0196] The swell characteristics of the lubricant oil compositions
is tested using the ASTM D4289 test procedure. Some engine oil
formulations have been shown to lack compatibility with certain
elastomers used for seals in automotive engines. These deleterious
effects on the elastomer are greatest with new engine oils (that
is, oils that have not been exposed to an engine's operating
environment) and when the exposure is at elevated temperatures.
ASTM D4289 is a test method that provides quantitative procedures
for the evaluation of the compatibility of automotive engine oils
with several reference elastomers typical of those used in the
sealing materials in contact with these oils. Compatibility is
evaluated by determining the changes in volume, Durometer A
hardness and tensile properties when the elastomer specimens are
immersed in the oil for a specified time and temperature.
[0197] Deposit Performance
[0198] Deposit Performance of the lubricant oil compositions is
measured using the TEOST MHT-4 (ASTM D7097) Thermo-Oxidation Engine
Oil Simulation Test ("TEOST"). The MHT-4 TEOST is a bench test
developed to determine piston deposit performance experienced when
engines are run under high power/high temperature conditions. The
deposit performance is measured in weight of deposit in mg.
[0199] Reserve Alkalinity
[0200] The reserve alkalinity of lubricant oil compositions is
tested using ASTM D2896, by determining the Total Base Number
("TBN"). TBN determines how effective the control of acids formed
is during the combustion process. The higher the TBN, the more
effective it is in suspending wear, causing contaminants and
reducing the corrosive effects of acids over an extended period of
time. The reserve alkalinity is measured in milligrams of potassium
hydroxide per gram (mg KOH/g).
[0201] Rust Preventing Qualities
[0202] The rust preventing qualities of lubricant oil compositions
is tested using the Ball Rust Test ("BRT") of ASTM D6557. The BRT
is an 18-hour bench test procedure in which a hydraulic lifter ball
in test oil is subjected to acids and air. The ball is rated
automatically for reflectance intensity as a measure of surface
area corrosion. The BRT is designed to evaluate an oil's ability to
inhibit rust of internal engine parts in cyclic cold and hot
operation where significant water and acid build-up can occur. The
rust preventing qualities is measured by gray value rating.
[0203] Levels of Ash-Forming Compounds
[0204] The levels of ash-forming compounds of lubricant oil
compositions is tested using ASTM D784. Sulfated ash is defined as
the residue remaining after an engine oil sample has been
carbonized (i.e., combusted), and the residue subsequently treated
with sulphuric acid and heated to constant weight. The primary
ash-forming materials in engine oils include calcium, magnesium,
sodium and potassium. These materials may be present in abrasive
solids, soluble metallic soaps and any remaining catalyst. Abrasive
solids and catalysts can lead to wear on injectors, fuel pumps,
pistons and rings, as well as engine deposits. Soluble metallic
soaps can also lead to engine deposits, as well as filter plugging.
The level of ash-forming compounds is determined by the weight of
residue remaining after the conclusion of the test.
[0205] The embodiments, described herein are intended to be merely
exemplary, and those skilled in the art will recognize, or be able
to ascertain using no more than routine experimentation, numerous
equivalents to the specific procedures described herein. All such
equivalents are considered to be within the scope of the present
invention and are covered by the following embodiments.
[0206] All references (including patent applications, patents, and
publications) cited herein are incorporated herein by reference in
their entirety and for all purposes to the same extent as if each
individual publication or patent or patent application was
specifically and individually indicated to be incorporated by
reference in its entirety for all purposes.
* * * * *
References