U.S. patent application number 16/275958 was filed with the patent office on 2020-01-23 for low viscosity low volatility benzoate monoester lubricating oil base stocks and methods of use thereof.
The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to Satish Bodige, Kyle G. Lewis, Abhimanyu O. Patil, Andrew D. Satterfield, Andrew E. Taggi.
Application Number | 20200024537 16/275958 |
Document ID | / |
Family ID | 65635831 |
Filed Date | 2020-01-23 |
![](/patent/app/20200024537/US20200024537A1-20200123-C00001.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00002.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00003.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00004.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00005.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00006.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00007.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00008.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00009.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00010.png)
![](/patent/app/20200024537/US20200024537A1-20200123-C00011.png)
View All Diagrams
United States Patent
Application |
20200024537 |
Kind Code |
A1 |
Patil; Abhimanyu O. ; et
al. |
January 23, 2020 |
LOW VISCOSITY LOW VOLATILITY BENZOATE MONOESTER LUBRICATING OIL
BASE STOCKS AND METHODS OF USE THEREOF
Abstract
A composition including one or more benzoate monoester compounds
represented by the formulae (I), (II), (III), (IV) and (V) as
defined herein. The composition has a viscosity (K.sub.V100) from
about 1 cSt to about 10 cSt at 100.degree. C. as determined by ASTM
D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800. A process for producing the
composition, a lubricating oil base stock and lubricating oil
containing the composition, and a method for improving one or more
of thermal and oxidative stability, solubility and dispersancy of
polar additives, deposit control and traction control in a
lubricating oil by using as the lubricating oil a formulated oil
containing the composition.
Inventors: |
Patil; Abhimanyu O.;
(Westfield, NJ) ; Lewis; Kyle G.; (Houston,
TX) ; Bodige; Satish; (Wayne, NJ) ; Taggi;
Andrew E.; (New Hope, PA) ; Satterfield; Andrew
D.; (Furlong, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company |
Annandale |
NJ |
US |
|
|
Family ID: |
65635831 |
Appl. No.: |
16/275958 |
Filed: |
February 14, 2019 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62633776 |
Feb 22, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 105/56 20130101;
C10N 2030/74 20200501; C10N 2030/02 20130101; C10M 107/02 20130101;
C10M 2207/2815 20130101; C10N 2030/54 20200501; C10M 2207/2845
20130101; C10N 2020/02 20130101; C10M 2215/003 20130101; C10M
105/34 20130101 |
International
Class: |
C10M 105/34 20060101
C10M105/34; C10M 105/56 20060101 C10M105/56; C10M 107/02 20060101
C10M107/02 |
Claims
1. A composition comprising one or more compounds represented by
the formula selected from the group consisting of ##STR00025##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
wherein said composition has a viscosity (K.sub.V100) from about 1
cSt to about 10 cSt at 100.degree. C. as determined by ASTM D445, a
viscosity index (VI) from about -100 to about 300 as determined by
ASTM D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
2. The composition of claim 1 which has a viscosity (K.sub.V100)
from about 2 cSt to about 8 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about 25 to about 150 as
determined by ASTM D2270, and a Noack volatility of no greater than
25 percent as determined by ASTM D5800.
3. The composition of claim 1, wherein the composition is selected
from the group consisting of 2-butyloctyl 4-butyl benzoate,
2-ethylhexyl 4-heptylbenzoate, butyloctyl 4-cyano benzoate,
2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl 2-methyl benzoate,
2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6 dimethyl benzoate,
2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl 2-methoxybenzoate,
2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl 4-methoxybenzoate,
2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl 3-fluorobenzoate,
2-hexyldecyl 4-fluorobenzoate, and combinations thereof.
4. A composition comprising one or more compounds represented by
the formula selected from the group consisting of ##STR00026##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
wherein said composition has a viscosity (K.sub.V100) from about 1
cSt to about 10 cSt at 100.degree. C. as determined by ASTM D445, a
viscosity index (VI) from about -100 to about 300 as determined by
ASTM D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800; wherein said compound of formula (I) is
produced by a process comprising reacting 2-butyloctanol with
4-butylbenzoic acid, optionally in the presence of a catalyst and a
solvent, under reaction conditions sufficient to produce the
compound of formula (I); or wherein said compound of formula (II)
is produced by a process comprising reacting 2-ethylhexanol with
4-heptylbenzoic acid, optionally in the presence of a catalyst and
a solvent, under reaction conditions sufficient to produce the
compound of formula (II); or wherein said compound of formula (III)
is produced by a process comprising reacting 2-butyloctanol with
4-nitrilebenzoic acid, optionally in the presence of a catalyst and
a solvent, under reaction conditions sufficient to produce the
compound of formula (III); or wherein said compound of formula (IV)
is produced by a process comprising reacting 2-hexyldecan-1-ol with
4-methylbenzoic acid, optionally in the presence of a catalyst and
a solvent, under reaction conditions sufficient to produce the
compound of formula (IV).
5. The composition of claim 4 which has a viscosity (K.sub.V100)
from about 2 cSt to about 8 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about 25 to about 150 as
determined by ASTM D2270, and a Noack volatility of no greater than
25 percent as determined by ASTM D5800.
6. A lubricating oil base stock comprising one or more compounds
represented by the formula selected from the group consisting of
##STR00027## wherein R.sub.2 is a H, F, methoxy, methyl or ethyl
group; R.sub.3 is a H, F, methoxy or methyl group; R.sub.4 is a H,
F methoxy or methyl group; R.sub.5 is H and R.sub.6 is H or a
methyl group wherein said lubricating oil base stock has a
viscosity (K.sub.V100) from about 1 cSt to about 10 cSt at
100.degree. C. as determined by ASTM D445, a viscosity index (VI)
from about -100 to about 300 as determined by ASTM D2270, and a
Noack volatility of no greater than 50 percent as determined by
ASTM D5800.
7. The lubricating oil base stock of claim 6 which has a viscosity
(K.sub.V100) from about 2 cSt to about 8 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about 25 to
about 150 as determined by ASTM D2270, and a Noack volatility of no
greater than 25 percent as determined by ASTM D5800.
8. The lubricating oil base stock of claim 6, wherein the
lubricating oil base stock is selected from the group consisting of
2-butyloctyl 4-butyl benzoate, 2-ethylhexyl 4-heptylbenzoate,
butyloctyl 4-cyano benzoate, 2-hexyldecyl 4-methyl benzoate,
2-hexyldecyl 2-methyl benzoate, 2-hexyldecyl 3-methyl benzoate,
2-hexyldecyl 2,6 dimethyl benzoate, 2-hexyldecyl 2-ethylbenzoate,
2-hexyldecyl 2-methoxybenzoate, 2-hexyldecyl 3-methoxybenzoate,
2-hexyldecyl 4-methoxybenzoate, 2-hexyldecyl 2-fluorobenzoate,
2-hexyldecyl 3-fluorobenzoate, 2-hexyldecyl 4-fluorobenzoate, and
combinations thereof.
9. The lubricating oil base stock of claim 6 further comprising one
or more of a viscosity improver, antioxidant, detergent,
dispersant, pour point depressant, corrosion inhibitor, metal
deactivator, seal compatibility additive, anti-foam agent,
inhibitor, and anti-rust additive.
10. A lubricating oil comprising a lubricating oil base stock
component, and a monoester cobase stock component; wherein said
monoester cobase stock comprises one or more compounds represented
by the formula selected from the group consisting of ##STR00028##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
wherein said lubricating oil has a viscosity (K.sub.V100) from
about 1 cSt to about 10 cSt at 100.degree. C. as determined by ASTM
D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800.
11. The lubricating oil of claim 10 wherein the lubricating oil
base stock comprises a Group I, II, III, IV or V base oil
stock.
12. The lubricating oil of claim 10 wherein the lubricating oil
base stock comprises a polyalphaolefin (PAO) or gas-to-liquid (GTL)
oil base stock.
13. The lubricating oil of claim 10 wherein the lubricating oil
base stock is present in an amount from about 1 weight percent to
about 99 weight percent, and the monoester cobase stock is present
in an amount from about 1 weight percent to about 99 weight
percent, based on the total weight of the lubricating oil.
14. The lubricating oil of claim 10 which has a viscosity
(K.sub.V100) from about 2 cSt to about 8 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about 25 to
about 150 as determined by ASTM D2270, and a Noack volatility of no
greater than 25 percent as determined by ASTM D5800.
15. The lubricating oil of claim 10, wherein the monoester cobase
stock is is selected from the group consisting of 2-butyloctyl
4-butyl benzoate, 2-ethylhexyl 4-heptylbenzoate, butyloctyl 4-cyano
benzoate, 2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl 2-methyl
benzoate, 2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6 dimethyl
benzoate, 2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl
2-methoxybenzoate, 2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl
4-methoxybenzoate, 2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl
3-fluorobenzoate, 2-hexyldecyl 4-fluorobenzoate, and combinations
thereof.
16. The lubricating oil of claim 10 further comprising one or more
of a viscosity improver, antioxidant, detergent, dispersant, pour
point depressant, corrosion inhibitor, metal deactivator, seal
compatibility additive, anti-foam agent, inhibitor, and anti-rust
additive.
17. A method for improving one or more of thermal and oxidative
stability, solubility and dispersancy of polar additives, deposit
control and traction control in a lubricating oil comprising:
providing a lubricating oil including a lubricating oil base stock
component, and a monoester cobase stock component; wherein said
monoester cobase stock comprises one or more compounds represented
by the formula selected from the group consisting of ##STR00029##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
wherein said lubricating oil has a viscosity (K.sub.V100) from
about 1 cSt to about 10 cSt at 100.degree. C. as determined by ASTM
D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800, and using the lubricating
oil in a formulated oil to improve one or more of thermal and
oxidative stability, solubility and dispersancy of polar additives,
deposit control and traction control.
18. The method of claim 17 wherein the lubricating oil base stock
comprises a Group I, II, III, IV or V base oil stock.
19. The method of claim 17 wherein the lubricating oil base stock
comprises a polyalphaolefin (PAO) or gas-to-liquid (GTL) oil base
stock.
20. The method of claim 17 wherein the lubricating oil base stock
is present in an amount from about 1 weight percent to about 99
weight percent, and the monoester cobase stock is present in an
amount from about 1 weight percent to about 99 weight percent,
based on the total weight of the lubricating oil.
21. The method of claim 17 wherein the lubricating oil has a
viscosity (K.sub.V100) from about 2 to about 8 at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about 25 to
about 150 as determined by ASTM D2270, and a Noack volatility of no
greater than 25 percent as determined by ASTM D5800.
22. The method of claim 17, wherein the monoester cobase stock is
selected from the group consisting of 2-butyloctyl 4-butyl
benzoate, 2-ethylhexyl 4-heptylbenzoate, butyloctyl 4-cyano
benzoate, 2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl 2-methyl
benzoate, 2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6 dimethyl
benzoate, 2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl
2-methoxybenzoate, 2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl
4-methoxybenzoate, 2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl
3-fluorobenzoate, 2-hexyldecyl 4-fluorobenzoate, and combinations
thereof.
23. The method of claim 17 wherein the lubricating oil further
comprises one or more of a viscosity improver, antioxidant,
detergent, dispersant, pour point depressant, corrosion inhibitor,
metal deactivator, seal compatibility additive, anti-foam agent,
inhibitor, and anti-rust additive.
24. A composition comprising one or more compounds represented by
the formula: ##STR00030## wherein X is a C.sub.1-C.sub.7 alkyl
group, a C.sub.1-C.sub.7 alkoxy group, a C.sub.1-C.sub.7 haloalkyl
group, a C.sub.1-C.sub.7 haloalkoxy group, a halogen, a cyano group
or a nitro group; n is from 1 to 5; P is from 1 to 12; Q is from 0
to 12; and P+Q is greater than 4, and wherein the composition has a
viscosity (K.sub.V100) from about 1 cSt to about 10 cSt at
100.degree. C. as determined by ASTM D445, a viscosity index (VI)
from about -100 to about 300 as determined by ASTM D2270, and a
Noack volatility of no greater than 50 percent as determined by
ASTM D5800.
25. The composition of claim 24 which has a viscosity (K.sub.V100)
from about 2 cSt to about 8 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about 25 to about 150 as
determined by ASTM D2270, and a Noack volatility of no greater than
25 percent as determined by ASTM D5800.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/633,776, filed on Feb. 22, 2018, the entire
contents of which are incorporated herein by reference.
FIELD
[0002] This disclosure relates to low viscosity, low volatility
compositions that include one or more benzoate monoester compounds,
a process for producing the compositions, a lubricating oil base
stock and lubricating oil containing the composition, and a method
for improving one or more of thermal and oxidative stability,
solubility and dispersancy of polar additives, deposit control and
traction control in a lubricating oil by using as the lubricating
oil a formulated oil containing the composition.
BACKGROUND
[0003] Lubricants in commercial use today are prepared from a
variety of natural and synthetic base stocks admixed with various
additive packages and solvents depending upon their intended
application. The base stocks typically include mineral oils,
polyalphaolefins (PAO), gas-to-liquid base oils (GTL), silicone
oils, phosphate esters, diesters, polyol esters, and the like.
[0004] A major trend for passenger car engine oils (PCEOs) is an
overall improvement in quality as higher quality base stocks become
more readily available. Typically the highest quality PCEO products
are formulated with base stocks such as PAOs or GTL stocks admixed
with various additive packages.
[0005] For improving fuel economy, base oil viscosity is very
important. Substantial improved fuel economy (>2%) requires
breakthrough in: (1) base oil volatility (2) durability and (3)
friction. Friction losses occur between the moving components
within the engine. Models developed to date indicate that fuel
economy is heavily influenced by the lubricant properties at high
shear. The base stock contributes a greater proportion of the total
viscosity under high shear conditions than under low shear.
Lowering base stock viscosity is likely to have the largest impact
on future fuel economy gains.
[0006] Current commercial PAO fluids (e.g., SpectraSyn.TM. 2) based
on hydrocarbon and commercial esters (e.g., 2-ethylhexyl adipate,
di-2-ethylhexyl azelate, Esterex.TM. A32, Esterex.TM. A34) do not
adequately allow formulation of ultra-low viscosity lubricant while
still meeting API specification (e.g., Noack volatility of 15% or
less). In order to formulate ultra-low viscosity lubricant for fuel
economy benefit, it is desirable to have low viscosity and low
volatility properties co-exist in the same base stock, for meeting
volatility requirement. In addition, the base stock should also
possess adequate thermal and oxidative stability at high
temperature to prevent or minimize deposit formation. Good
compatibility with additives commonly used in lubricant
formulations (PVL--Passenger Vehicle Lubricants, CVL--Commercial
Vehicle Lubricants, industrial lubricants), good low temperature
properties, and acceptable viscosity indices are also necessary for
the base stocks.
[0007] Poly-.alpha.-olefins (PAOs) are important lube base stocks
with many excellent lubricant properties, including high viscosity
index (VI), low volatility and are available in various viscosity
range (K.sub.V100 2-300 cSt). However, PAOs are paraffinic
hydrocarbons with low polarity. This low polarity leads to low
solubility and dispersancy for polar additives or sludge generated
during service. To compensate for this low polarity, lube
formulators usually add one or multiple polar cobase stocks. Ester
or alkylated naphthalene (AN) is usually present at 1 wt. % to 50
wt. % levels in many finished lubricant formulations to increase
the fluid polarity which improves the solubility of polar additives
and sludge.
[0008] Therefore, there is a need for polar cobase fluids that
provide appropriate solubility and dispersibility for polar
additives or sludge generated during service of lubricating
oils.
[0009] Future automotive and industrial trend suggest that there
will be a need for advanced additive technology and synthetic base
stocks with substantially better thermal and oxidative stability.
This is primarily because of smaller sump sizes that will have more
thermal and oxidative stresses on the lubricants. Performance
requirements have become more stringent in the past 10 to 20 years
and the demand for longer drain intervals has grown steadily. Also,
the use of Group II, III and IV base oils is becoming more
widespread. Such base oils have very little sulfur content since
natural sulfur-containing antioxidants are either absent or removed
during the severe refining process.
[0010] It is known that lubricant oils used in internal combustion
engines and transmission of automobile engines or trucks are
subjected to demanding environments during use. These environments
result in the lubricant suffering oxidation catalyzed by the
presence of impurities in the oil, such as iron (wear) compounds
and elevated temperatures. The oxidation manifests itself by
increase in acid or viscosity and deposit formation or any
combination of these symptoms. These are controlled to some extent
by the use of antioxidants which can extend the useful life of the
lubricating oil, particularly by reducing or preventing
unacceptable viscosity increases. Besides oxidation inhibition,
other parameters such as rust and wear control are also
important.
[0011] A major challenge in engine oil formulation is
simultaneously achieving improved fuel economy while also achieving
appropriate solubility and dispersibility for polar additives or
sludge generated during service of lubricating oils and oxidative
stability.
[0012] Therefore, there is need for better additive and base stock
technology for lubricant compositions that will meet ever more
stringent requirements of lubricant users. In particular, there is
a need for advanced additive technology and synthetic base stocks
with improved fuel economy, solubility and dispersibility for polar
additives or sludge generated during service of lubricating oils,
and oxidative stability.
[0013] The present disclosure also provides many additional
advantages, which shall become apparent as described below.
SUMMARY
[0014] This disclosure provides compositions that include one or
more benzoate monoesters that have desirable low viscosity/low
volatility properties while exhibiting good high-temperature
thermal-oxidative stability. Thus, the lubricating oil base stocks
of this disclosure provide a solution to achieve enhanced fuel
economy and energy efficiency. In addition, good solvency for
commonly used polar additives and potentially good hydrolytic,
thermal and oxidative stability, deposit control and traction
control are other advantages of these compositions.
[0015] This disclosure relates in part to a composition comprising
one or more compounds represented by the formula selected from the
group consisting of
##STR00001##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0016] This disclosure also relates in part to a composition
comprising one or more compounds represented by the formula
selected from the group consisting of
##STR00002##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group.
[0017] The composition has a viscosity (K.sub.V100) from about 1
cSt to about 10 cSt at 100.degree. C. as determined by ASTM D445, a
viscosity index (VI) from about -100 to about 300 as determined by
ASTM D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800. The compound of formula (I) is produced
by a process comprising reacting 2-butyloctanol with 4-butylbenzoic
acid, optionally in the presence of a catalyst and a solvent, under
reaction conditions sufficient to produce the compound of formula
(I). The compound of formula (II) is produced by a process
comprising reacting 2-ethylhexanol with 4-heptylbenzoic acid,
optionally in the presence of a catalyst and a solvent, under
reaction conditions sufficient to produce the compound of formula
(II). The compound of formula (III) is produced by a process
comprising reacting 2-butyloctanol with 4-nitrilebenzoic acid,
optionally in the presence of a catalyst and a solvent, under
reaction conditions sufficient to produce the compound of formula
(III). The compound of formula (IV) is produced by a process
comprising reacting 2-hexyldecan-1-ol with 4-methylbenzoic acid,
optionally in the presence of a catalyst and a solvent, under
reaction conditions sufficient to produce the compound of formula
(IV).
[0018] This disclosure further relates in part to a lubricating oil
base stock comprising one or more compounds represented by the
formula selected from the group consisting of
##STR00003##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0019] This disclosure yet further relates in part to a lubricating
oil comprising a lubricating oil base stock component, and a
monoester cobase stock component; wherein said monoester cobase
stock comprises one or more compounds represented by the formula
selected from the group consisting of
##STR00004##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0020] This disclosure also relates in part to a method for
improving one or more of thermal and oxidative stability,
solubility and dispersancy of polar additives, deposit control and
traction control in a lubricating oil by using as the lubricating
oil a formulated oil comprising a lubricating oil base stock as a
major component, and a monoester cobase stock as a minor component;
wherein said monoester cobase stock comprises one or more compounds
represented by the formula selected from the group consisting
of
##STR00005##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0021] This disclosure also relates in part to a composition
comprising one or more compounds represented by the formula:
##STR00006##
wherein X is a C.sub.1-C.sub.7 alkyl group, a C.sub.1-C.sub.7
alkoxy group, a C.sub.1-C.sub.7 haloalkyl group, a C.sub.1-C.sub.7
haloalkoxy group, a halogen, a cyano group or a nitro group; n is
from 1 to 5; P is from 1 to 12; Q is from 0 to 12; and wherein P+Q
is greater than 4. The composition has a viscosity (K.sub.V100)
from about 1 cSt to about 10 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800.
[0022] It has been surprisingly found that outstanding low
viscosity low volatility properties, good high-temperature thermal
and oxidative stability, good solvency for polar additives, deposit
control, and traction benefits, can be attained in an engine
lubricated with a lubricating oil by using as the lubricating oil a
formulated oil in accordance with this disclosure. In particular, a
lubricating oil base stock comprising one or more benzoate
monoesters exhibits low viscosity, low volatility, desired solvency
for polar additives, superior oxidative stability, desired deposit
control and traction benefits, which helps to prolong the useful
life of lubricants and significantly improve the durability and
resistance of lubricants when exposed to high temperatures.
[0023] The lubricating oils of this disclosure are particularly
advantageous as passenger vehicle engine oil (PVEO) products, more
specifically SAE 0WX, SAE 5WX, or SAE 10WX, (where X=4, 8, 12, 16,
20, 30, 40, or 50), and similar oil formulations, especially oil
formulations exhibiting lowered volatility when blended with the
components of this invention. Furthermore, the esters of this
invention can be used in low ash, low metals, low phosphorus oils,
preferably formulated with ZDDP derived in part from secondary
alcohols, with metallic detergents, such as salicylates, phenates
and/or sulfonates, preferably magnesium and/or calcium, with
succinimide dispersants or with boron-containing detergents or
dispersants.
[0024] Further objects, features and advantages of the present
disclosure will be understood by reference to the following
drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 shows lube properties including kinematic
viscosities, viscosity indices (VI) and volatility of benzoate
monoester base stocks of this disclosure in accordance with the
Examples.
[0026] FIG. 2 shows the structure (R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, molecular ion) and properties (KV40, KV100) of
the exemplary compound (V) benzoate monoester base stocks of this
disclosure.
DETAILED DESCRIPTION
[0027] All numerical values within the detailed description and the
claims herein are modified by "about" or "approximately" the
indicated value, and take into account experimental error and
variations that would be expected by a person having ordinary skill
in the art. The phrase "major amount" or "major component" as it
relates to components included within the lubricating oils of the
specification and the claims means greater than or equal to 50 wt.
%, or greater than or equal to 60 wt. %, or greater than or equal
to 70 wt. %, or greater than or equal to 80 wt. %, or greater than
or equal to 90 wt. % based on the total weight of the lubricating
oil. The phrase "minor amount" or "minor component" as it relates
to components included within the lubricating oils of the
specification and the claims means less than 50 wt. %, or less than
or equal to 40 wt. %, or less than or equal to 30 wt. %, or greater
than or equal to 20 wt. %, or less than or equal to 10 wt. %, or
less than or equal to 5 wt. %, or less than or equal to 2 wt. %, or
less than or equal to 1 wt. %, based on the total weight of the
lubricating oil. The phrase "essentially free" as it relates to
components included within the lubricating oils of the
specification and the claims means that the particular component is
at 0 weight % within the lubricating oil, or alternatively is at
impurity type levels within the lubricating oil (less than 100 ppm,
or less than 20 ppm, or less than 10 ppm, or less than 1 ppm). The
phrase "other lubricating oil additives" as used in the
specification and the claims means other lubricating oil additives
that are not specifically recited in the particular section of the
specification or the claims. For example, other lubricating oil
additives may include, but are not limited to, an anti-wear
additive, viscosity improver or modifier, antioxidant, detergent,
dispersant, pour point depressant, corrosion inhibitor, metal
deactivator, seal compatibility additive, anti-foam agent,
inhibitor, anti-rust additive, friction modifier and combinations
thereof.
[0028] The compositions of this disclosure are benzoate monoesters.
A benzoate monoester is defined as a compound with ester
functionality directly linked to an aryl group. These compositions
exhibit (1) outstanding low viscosity low volatility properties,
(2) good high-temperature thermal and oxidative stability, (3) good
solvency for polar additives, (4) good deposit control, and (5)
traction benefits, which make them attractive as Group V synthetic
base stocks in high performance, fuel economy lubricant
applications.
[0029] Low viscosity base stocks (e.g., kinematic viscosity at
100.degree. C., 2-3 cSt) currently available in the marketplace are
too volatile (Noack >15-20%) to be used for formulating
next-generation ultra-low viscosity engine oils (i.e.,
xxW-4.fwdarw.xxW-16). These base stocks (e.g., SpectraSyn.TM. 2,
QHVI' 3, bis-(2-ethylhexyl) adipate, di-2-ethylhexyl azelate,
Esterex.TM. A32) are unable to provide formulated engine oils that
also meet current volatility API specification. In addition,
current Group V ester base stocks generally have poor high
temperature oxidation stability which can cause operational
problems in engine, potentially causing high deposit formation. The
present disclosure identifies benzoate monoesters that have
desirable low viscosity and low volatility properties while
exhibiting traction benefits, good deposit control behavior and
good high-temperature thermal-oxidative stability, hence provides a
solution to achieve enhanced fuel economy and energy efficiency. In
addition, good solvency for commonly used polar additives and
potentially good hydrolytic stability are other advantages of these
compounds in base stock applications.
[0030] As indicated above, the compositions of this disclosure
include, for example, one or more benzoate monoester compounds
represented by the formula selected from the group consisting
of
##STR00007##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0031] The compositions of this disclosure may also include, for
example, one or more benzoate monoester compounds represented by
the formula:
##STR00008##
wherein X is a C.sub.1-C.sub.7 alkyl group, a C.sub.1-C.sub.7
alkoxy group, a C.sub.1-C.sub.7 haloalkyl group, a C.sub.1-C.sub.7
haloalkoxy group, a halogen, a cyano group or a nitro group; n is
from 1 to 5; P is from 1 to 12; Q is from 0 to 12; and wherein P+Q
is greater than 4. The composition has a viscosity (K.sub.V100)
from about 1 cSt to about 10 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800.
[0032] Illustrative benzoate monoester compositions of this
disclosure have a viscosity (K.sub.V100) from about 1 cSt to about
8 cSt, more preferably from about 2 cSt to about 6 cSt, at
100.degree. C. as determined by ASTM D445, a viscosity index (VI)
from about -100 to about 300, more preferably from about 0 to about
200, even more preferably from about 25 to about 150, as determined
by ASTM D2270, a Noack volatility of no greater than 50 percent, or
no greater than 25 percent, more preferably no greater than 20
percent, even more preferably no greater than 15 percent, as
determined by ASTM D5800. The lower limit of the Noack volatility
as determined by ASTM D5800 may be greater than or equal to 1
percent, or greater than or equal to 3 percent, or greater than or
equal to 5 percent, or greater than or equal to 8 percent, or
greater than or equal to 10 percent, or greater than or equal to 15
percent, or greater than or equal to 20 percent.
[0033] Illustrative benzoate monoester compositions of this
disclosure include, for example, 2-butyloctyl 4-butyl benzoate,
2-ethylhexyl 4-heptylbenzoate, butyloctyl 4-cyano benzoate,
2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl 2-methyl benzoate,
2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6 dimethyl benzoate,
2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl 2-methoxybenzoate,
2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl 4-methoxybenzoate,
2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl 3-fluorobenzoate,
2-hexyldecyl 4-fluorobenzoate, combinations thereof, and the
like.
[0034] The benzoate monoester compositions of the present
disclosure can be prepared by a process that involves reacting a
substituted or unsubstituted alcohol with a substituted or
unsubstituted benzoic acid, optionally in the presence of a
catalyst, under reaction conditions sufficient to produce one or
more benzoate monoester compositions.
[0035] Illustrative alcohols useful in the process of this
disclosure include, for example, 2-heptyl-1-undecanol,
2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-octyl-1-decanol,
2-octyl-1-dodecanol, 2-butyl-1-octanol, 2-decyl-1-dodecanol,
2-decyl-1-tetradecanol, 2-ethyl-1-hexanol, 2-butyl-1-hexanol,
isopropanol, 2-methylbutanol, 2-methyl-1-pentanol, isotridecanol,
isodecanol, isononanol, isooctanol, alcohols obtained from
hydroformylation of terminal monosubstituted alkenes,
1,1-disubstituted alkenes, cis- or trans-1,2-disubstituted alkenes
using carbon monoxide, hydrogen and a suitable transition metal
catalyst, followed by hydrogenation (commonly known as oxo
alcohols), and the like. Examples of commercially available oxo
alcohols are, but not limited to, Exxal.TM. alcohols manufactured
and marketed by ExxonMobil Corporation). Particularly preferred
alcohols useful in the process of this disclosure include
2-butyloctanol, 2-ethylhexanol, and 2-hexyldecan-1-ol.
[0036] Illustrative benzoic acids useful in the process of this
disclosure include, for example, 4-butyllbenzoic acid,
4-heptylbenzoic acid, 4-nitrilebenzoic acid, 4-methylbenzoic acid,
2,4,5-trimethyl benzoic acid, 2,4,6-trimethyl benzoic acid,
4-isopropyl benzoic acid, 3,5-dimethyl-4-methoxy benzoic acid,
4-propoxyl benzoic acid, 4-tert butyl benzoic acid, 4-butoxy
benzoic acid, 2,4-diethoxy benzoic acid, 2,4-diethoxy benzoic acid,
2.5-diethoxy benzoic acid, 2,5-dimethyl-benzoic acid,
2,6-dimethyl-benzoic acid, 3,4-dimethyl-benzoic acid,
35-dimethyl-benzoic acid, 4-octylbenzoic acid, 3-cyanobenzoic acid,
2-cyanobenzoic acid, 4-ethylbenzoic acid, 2-ethylbenzoic acid,
4-ethoxybenzoic acid, 4-pentylbenzoic acid, 4-(decyloxy)bezoic
acid, 4-(heptyloxy)benzoic acid, 4-(octyloxy)benzic acid,
4-(dodecyloxy)benzoic acid, 3-methylbenzoic acid, 2-menthylbenzoic
acid, 4-nirtobenzoic acid, 3-nitrobenzoic acid, 2-nitrobenzoic
acid, and the like.
[0037] Reaction conditions for the reaction of the alcohol with the
benzoic acid, such as temperature, pressure and contact time, may
also vary greatly and any suitable combination of such conditions
may be employed herein. The reaction temperature may range between
about 25.degree. C. to about 300.degree. C., and preferably between
about 50.degree. C. to about 250.degree. C., and more preferably
between about 100.degree. C. to about 200.degree. C. Normally the
reaction is carried out under ambient pressure and the contact time
may vary from a matter of seconds or minutes to a few hours or
greater. The reactants can be added to the reaction mixture or
combined in any order. The reaction residence time employed can
range from about 30 seconds to about 48 hours, preferably from
about 5 minutes to 36 hours, and more preferably from about 1 hour
to 24 hours.
[0038] As shown in the Examples herein, the benzoate monoester
compositions of formulae (I), (II), (III), (IV) and (V) have more
desirable viscosity-volatility characteristics when compared to
commercially available low viscosity Group IV PAO synthetic base
stocks (e.g., SpectraSyn.TM. 2, SpectraSyn.TM. 4) or Group V ester
base stocks (e.g., 2-ethylhexyl oleate, 2-ethylhexyl adipate,
isodecyl adipate, 2-ethylhexyl phthalate, nC8/nC10 neopentyl glycol
esters, nC7 trimethyolpropane ester, and the like). As shown in the
Examples herein, the benzoate monoester compositions of formulae
(I), (II), (III), (IV) and (V) of the present disclosure have lower
viscosities than commercially available esters at similar
volatility. Additionally, the benzoate monoester compositions of
formulae I), (II), (III), (IV) and (V) have lower volatility than
commercially available esters at comparable viscosities.
[0039] Furthermore, it has been found that these benzoate monoester
compositions of formulae (I), (II), (III), (IV) and (V) also show
high solvency for the typical additive components (e.g., antiwear
additives, friction modifiers, dispersants, detergents,
antioxidants, viscosity modifiers, pour point depressants,
antifoaming agent, etc.) employed in the formulation of PVL
(Passenger Vehicles Lubricants), CVL (Commercial Vehicles
Lubricants), as well as industrial applications.
[0040] Examples of techniques that can be employed to characterize
the compositions formed by the process described above include, but
are not limited to, analytical gas chromatography, nuclear magnetic
resonance, thermogravimetric analysis (TGA), inductively coupled
plasma mass spectrometry, differential scanning calorimetry (DSC),
volatility and viscosity measurements.
[0041] This disclosure provides lubricating oils useful as engine
oils and in other applications characterized by excellent oxidative
stability. The lubricating oils are based on high quality base
stocks including a major portion of a hydrocarbon base fluid such
as a PAO or GTL with a secondary cobase stock component which is a
monoester as described herein. The lubricating oil base stock can
be any oil boiling in the lube oil boiling range, typically between
about 100 to 450.degree. C. In the present specification and
claims, the terms base oil(s) and base stock(s) are used
interchangeably.
[0042] The viscosity-temperature relationship of a lubricating oil
is one of the critical criteria which must be considered when
selecting a lubricant for a particular application. Viscosity Index
(VI) is an empirical, unitless number which indicates the rate of
change in the viscosity of an oil within a given temperature range.
Fluids exhibiting a relatively large change in viscosity with
temperature are said to have a low viscosity index. A low VI oil,
for example, will thin out at elevated temperatures faster than a
high VI oil. Usually, the high VI oil is more desirable because it
has higher viscosity at higher temperature, which translates into
better or thicker lubrication film and better protection of the
contacting machine elements.
[0043] In another aspect, as the oil operating temperature
decreases, the viscosity of a high VI oil will not increase as much
as the viscosity of a low VI oil. This is advantageous because the
excessive high viscosity of the low VI oil will decrease the
efficiency of the operating machine. Thus high VI (HVI) oil has
performance advantages in both high and low temperature operation.
VI is determined according to ASTM D2270. VI is related to
kinematic viscosities measured at 40.degree. C. and 100.degree. C.
using ASTM D445.
Lubricating Oil Base Stocks
[0044] A wide range of lubricating oils is known in the art.
Lubricating oils that are useful in the present disclosure are both
natural oils and synthetic oils. Natural and synthetic oils (or
mixtures thereof) can be used unrefined, refined, or rerefined (the
latter is also known as reclaimed or reprocessed oil). Unrefined
oils are those obtained directly from a natural or synthetic source
and used without added purification. These include shale oil
obtained directly from retorting operations, petroleum oil obtained
directly from primary distillation, and ester oil obtained directly
from an esterification process. Refined oils are similar to the
oils discussed for unrefined oils except refined oils are subjected
to one or more purification steps to improve the at least one
lubricating oil property. One skilled in the art is familiar with
many purification processes. These processes include solvent
extraction, secondary distillation, acid extraction, base
extraction, filtration, and percolation. Rerefined oils are
obtained by processes analogous to refined oils but using an oil
that has been previously used as a feed stock.
[0045] Groups I, II, III, IV and V are broad categories of base oil
stocks developed and defined by the American Petroleum Institute
(API Publication 1509; www.API.org) to create guidelines for
lubricant base oils. Group I base stocks generally have a viscosity
index of between about 80 to 120 and contain greater than about
0.03% sulfur and less than about 90% saturates. Group II base
stocks generally have a viscosity index of between about 80 to 120,
and contain less than or equal to about 0.03% sulfur and greater
than or equal to about 90% saturates. Group III stock generally has
a viscosity index greater than about 120 and contains less than or
equal to about 0.03% sulfur and greater than about 90% saturates.
Group IV includes polyalphaolefins (PAO). Group V base stocks
include base stocks not included in Groups I-IV. The table below
summarizes properties of each of these five groups.
TABLE-US-00001 Base Oil Properties Saturates Sulfur Viscosity Index
Group I <90 and/or >0.03% and .gtoreq.80 and <120 Group II
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.80 and <120 Group III
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.120 .sub. Group IV
Includes polyalphaolefins (PAO) products Group V All other base oil
stocks not included in Groups I, II, III or IV
[0046] Natural oils include animal oils, vegetable oils (castor oil
and lard oil, for example), and mineral oils. Animal and vegetable
oils possessing favorable thermal oxidative stability can be used.
Of the natural oils, mineral oils are preferred. Mineral oils vary
widely as to their crude source, for example, as to whether they
are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils
derived from coal or shale are also useful in the present
disclosure. Natural oils vary also as to the method used for their
production and purification, for example, their distillation range
and whether they are straight run or cracked, hydrorefined, or
solvent extracted.
[0047] Group II and/or Group III hydroprocessed or hydrocracked
base stocks, as well as synthetic oils such as polyalphaolefins,
alkyl aromatics and synthetic esters, i.e. Group IV and Group V
oils are also well known base stock oils.
[0048] Synthetic oils include hydrocarbon oil such as polymerized
and interpolymerized olefins (polybutylenes, polypropylenes,
propylene isobutylene copolymers, ethylene-olefin copolymers, and
ethylene-alphaolefin copolymers, for example). Polyalphaolefin
(PAO) oil base stocks, the Group IV API base stocks, are a commonly
used synthetic hydrocarbon oil. By way of example, PAOs derived
from C.sub.8, C.sub.10, C.sub.12, C.sub.14 olefins or mixtures
thereof may be utilized. See U.S. Pat. Nos. 4,956,122; 4,827,064;
and 4,827,073, which are incorporated herein by reference in their
entirety. Group IV oils, that is, the PAO base stocks have
viscosity indices preferably greater than 130, more preferably
greater than 135, still more preferably greater than 140.
[0049] Esters may be useful in the lubricating oils of this
disclosure. 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
monocarboxylic acids. Esters of the former type include, for
example, the esters of dicarboxylic acids such as phthalic acid,
succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid,
etc., with a variety of alcohols such as butyl alcohol, hexyl
alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specific
examples of these types of esters include dibutyl adipate,
di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, etc.
[0050] Particularly useful synthetic esters are those which are
obtained by reacting one or more polyhydric alcohols, preferably
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, preferably
C.sub.5 to C.sub.30 acids such as saturated straight chain fatty
acids including caprylic acid, capric acids, lauric acid, myristic
acid, palmitic acid, stearic acid, arachic acid, and behenic acid,
or the corresponding branched chain fatty acids or unsaturated
fatty acids such as oleic acid, or mixtures of any of these
materials.
[0051] Esters should be used in an amount such that the improved
wear and corrosion resistance provided by the lubricating oils of
this disclosure are not adversely affected.
[0052] Non-conventional or unconventional base stocks and/or base
oils include one or a mixture of base stock(s) and/or base oil(s)
derived from: (1) one or more Gas-to-Liquids (GTL) materials, as
well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent)
dewaxed base stock(s) and/or base oils derived from synthetic wax,
natural wax or waxy feeds, mineral and/or non-mineral oil waxy feed
stocks such as gas oils, slack waxes (derived from the solvent
dewaxing of natural oils, mineral oils or synthetic oils; e.g.,
Fischer-Tropsch feed stocks), natural waxes, and waxy stocks such
as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate,
hydrocrackate, thermal crackates, foots oil or other mineral,
mineral oil, or even non-petroleum oil derived waxy materials such
as waxy materials recovered from coal liquefaction or shale oil,
linear or branched hydrocarbyl compounds with carbon number of
about 20 or greater, preferably about 30 or greater and mixtures of
such base stocks and/or base oils.
[0053] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and/or base oils
are GTL materials of lubricating viscosity that are generally
derived from hydrocarbons; for example, waxy synthesized
hydrocarbons, that are themselves derived from simpler gaseous
carbon-containing compounds, hydrogen-containing compounds and/or
elements as feed stocks. GTL base stock(s) and/or base oil(s)
include oils boiling in the lube oil boiling range (1)
separated/fractionated from synthesized GTL materials such as, for
example, by distillation and subsequently subjected to a final wax
processing step which involves either or both of a catalytic
dewaxing process, or a solvent dewaxing process, to produce lube
oils of reduced/low pour point; (2) synthesized wax isomerates,
comprising, for example, hydrodewaxed or hydroisomerized cat and/or
solvent dewaxed synthesized wax or waxy hydrocarbons; (3)
hydrodewaxed or hydroisomerized cat and/or solvent dewaxed
Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); preferably
hydrodewaxed or hydroisomerized/followed by cat and/or solvent
dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T
waxes, or mixtures thereof.
[0054] GTL base stock(s) and/or base oil(s) derived from GTL
materials, especially, hydrodewaxed or hydroisomerized/followed by
cat and/or solvent dewaxed wax or waxy feed, preferably F-T
material derived base stock(s) and/or base oil(s), are
characterized typically as having kinematic viscosities at
100.degree. C. of from about 2 mm.sup.2/s to about 50 mm.sup.2/s
(ASTM D445). They are further characterized typically as having
pour points of -5.degree. C. to about -40.degree. C. or lower (ASTM
D97). They are also characterized typically as having viscosity
indices of about 80 to about 140 or greater (ASTM D2270).
[0055] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) typically have very low sulfur and
nitrogen content, generally containing less than about 10 ppm, and
more typically less than about 5 ppm of each of these elements. The
sulfur and nitrogen content of GTL base stock(s) and/or base oil(s)
obtained from F-T material, especially F-T wax, is essentially nil.
In addition, the absence of phosphorous and aromatics make this
materially especially suitable for the formulation of low SAP
products.
[0056] The term GTL base stock and/or base oil and/or wax isomerate
base stock and/or base oil is to be understood as embracing
individual fractions of such materials of wide viscosity range as
recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low
viscosity fractions with one, two or more higher viscosity
fractions to produce a blend wherein the blend exhibits a target
kinematic viscosity.
[0057] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived is preferably an F-T material (i.e.,
hydrocarbons, waxy hydrocarbons, wax).
[0058] Base oils for use in the formulated lubricating oils useful
in the present disclosure are any of the variety of oils
corresponding to API Group I, Group II, Group III, Group IV, Group
V and Group VI oils and mixtures thereof, preferably API Group II,
Group III, Group IV, Group V and Group VI oils and mixtures
thereof, more preferably the Group III to Group VI base oils due to
their exceptional volatility, stability, viscometric and
cleanliness features. Minor quantities of Group I stock, such as
the amount used to dilute additives for blending into formulated
lube oil products, can be tolerated but should be kept to a
minimum, i.e. amounts only associated with their use as
diluent/carrier oil for additives used on an "as received" basis.
Even in regard to the Group II stocks, it is preferred that the
Group II stock be in the higher quality range associated with that
stock, i.e. a Group II stock having a viscosity index in the range
100<VI<120.
[0059] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) and hydrodewaxed, or
hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or
base oil(s) typically have very low sulfur and nitrogen content,
generally containing less than about 10 ppm, and more typically
less than about 5 ppm of each of these elements. The sulfur and
nitrogen content of GTL base stock(s) and/or base oil(s) obtained
from F-T material, especially F-T wax, is essentially nil. In
addition, the absence of phosphorous and aromatics make this
material especially suitable for the formulation of low sulfur,
sulfated ash, and phosphorus (low SAP) products.
[0060] The base stock component of the present lubricating oils
will typically be from 1 to 99 weight percent of the total
composition (all proportions and percentages set out in this
specification are by weight unless the contrary is stated) and more
preferably in the range of 10 to 99 weight percent, or more
preferably from 15 to 80 percent, or more preferably from 20 to 70
percent, or more preferably from 25 to 60 percent, or more
preferably from 30 to 50 percent.
Benzoate Monoester Base Stock and Cobase Stock Components
[0061] Benzoate monoester base stock and cobase stock components
useful in this disclosure include, for example, compositions
containing one or more compounds represented by the formula
selected from the group consisting of
##STR00009##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group. The
composition has a viscosity (K.sub.V100) from about 1 cSt to about
10 cSt at 100.degree. C. as determined by ASTM D445, a viscosity
index (VI) from about -100 to about 300 as determined by ASTM
D2270, and a Noack volatility of no greater than 50 percent as
determined by ASTM D5800.
[0062] Illustrative benzoate monoester base stock and cobase stock
components of this disclosure have a viscosity (K.sub.V100) from
about 1 cSt to about 8 cSt, more preferably from about 2 cSt to
about 6 cSt, at 100.degree. C. as determined by ASTM D445, a
viscosity index (VI) from about -100 to about 300, more preferably
from about 0 to about 200, even more preferably from about 25 to
about 150, as determined by ASTM D2270, a Noack volatility of no
greater than 25 percent, more preferably no greater than 20
percent, even more preferably no greater than 15 percent, as
determined by ASTM D5800, and a high temperature high shear (HTHS)
viscosity of less than about 2.5 cP, more preferably less than
about 2.25 cP, even more preferably less than about 2.0 cP, as
determined by ASTM D4683.
[0063] Preferred benzoate monoester base stock and cobase stock
components of this disclosure have a high temperature high shear
(HTHS) viscosity of less than about 1.7 cP as determined by ASTM
D4683, and a Noack volatility from about 15 percent to about 30
percent as determined by ASTM D5800.
[0064] Illustrative benzoate monoester base stock and cobase stock
components of this disclosure include, for example, 2-butyloctyl
4-butyl benzoate, 2-ethylhexyl 4-heptylbenzoate, butyloctyl 4-cyano
benzoate, 2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl 2-methyl
benzoate, 2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6 dimethyl
benzoate, 2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl
2-methoxybenzoate, 2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl
4-methoxybenzoate, 2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl
3-fluorobenzoate, 2-hexyldecyl 4-fluorobenzoate, combinations
thereof, and the like.
[0065] The benzoate monoester base stock and cobase stock
components of the present disclosure can be prepared by a process
that involves reacting a substituted or unsubstituted alcohol with
a substituted or unsubstituted benzoic acid, optionally in the
presence of a catalyst, under reaction conditions sufficient to
produce one or more benzoate monoester compositions.
[0066] Illustrative alcohols useful in the process of this
disclosure include, for example, 2-heptyl-1-undecanol,
2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-octyl-1-decanol,
2-octyl-1-dodecanol, 2-butyl-1-octanol, 2-decyl-1-dodecanol,
2-decyl-1-tetradecanol, 2-ethyl-1-hexanol, 2-butyl-1-hexanol,
isopropanol, 2-methylbutanol, 2-methyl-1-pentanol, isotridecanol,
isodecanol, isononanol, isooctanol, alcohols obtained from
hydroformylation of terminal monosubstituted alkenes,
1,1-disubstituted alkenes, cis- or trans-1,2-disubstituted alkenes
using carbon monoxide, hydrogen and a suitable transition metal
catalyst, followed by hydrogenation (commonly known as oxo
alcohols), and the like. Examples of commercially available oxo
alcohols are, but not limited to, Exxal.TM. alcohols manufactured
and marketed by ExxonMobil Corporation). Particularly preferred
alcohols useful in the process of this disclosure include
2-butyloctanol, 2-ethylhexanol, and 2-hexyldecan-1-ol.
[0067] Illustrative benzoic acids useful in the process of this
disclosure include, for example, 4-butyllbenzoic acid,
4-heptylbenzoic acid, 4-nitrilebenzoic acid, 4-methylbenzoic acid,
2,4,5-trimethyl benzoic acid, 2,4,6-trimethyl benzoic acid,
4-isopropyl benzoic acid, 3,5-dimethyl-4-methoxy benzoic acid,
4-propoxyl benzoic acid, 4-tert butyl benzoic acid, 4-butoxy
benzoic acid, 2,4-diethoxy benzoic acid, 2,4-diethoxy benzoic acid,
2.5-diethoxy benzoic acid, 2,5-dimethyl-benzoic acid,
2,6-dimethyl-benzoic acid, 3,4-dimethyl-benzoic acid,
35-dimethyl-benzoic acid, 4-octylbenzoic acid, 3-cyanobenzoic acid,
2-cyanobenzoic acid, 4-ethylbenzoic acid, 2-ethylbenzoic acid,
4-ethoxybenzoic acid, 4-pentylbenzoic acid, 4-(decyloxy)bezoic
acid, 4-(heptyloxy)benzoic acid, 4-(octyloxy)benzic acid,
4-(dodecyloxy)benzoic acid, 3-methylbenzoic acid, 2-menthylbenzoic
acid, 4-nirtobenzoic acid, 3-nitrobenzoic acid, 2-nitrobenzoic
acid, and the like.
[0068] Reaction conditions for the reaction of the alcohol with the
benzoic acid, such as temperature, pressure and contact time, may
also vary greatly and any suitable combination of such conditions
may be employed herein. The reaction temperature may range between
about 25.degree. C. to about 300.degree. C., and preferably between
about 50.degree. C. to about 250.degree. C., and more preferably
between about 100.degree. C. to about 200.degree. C. Normally the
reaction is carried out under ambient pressure and the contact time
may vary from a matter of seconds or minutes to a few hours or
greater. The reactants can be added to the reaction mixture or
combined in any order. The reaction residence time employed can
range from about 30 seconds to about 48 hours, preferably from
about 5 minutes to 36 hours, and more preferably from about 1 hour
to 24 hours.
[0069] The monoester base stock component is preferably present in
an amount sufficient for providing oxidative stability in the
lubricating oil. The monoester base stock component can be present
as the major base stock in the lubricating oils of this disclosure.
Accordingly, the monoester can be present in an amount from about 1
to about 99 weight percent, preferably from about 5 to about 99
weight percent, and more preferably from about 10 to about 99
weight percent, or more preferably from about 40 to about 90 weight
percent, or more preferably from about 50 to about 80 weight
percent, or more preferably from about 60 to about 80 weight
percent.
[0070] The monoester base stock component can also be present as a
minor co-base stock in the lubricating oils of this disclosure.
Accordingly, the monoester co-base stock component of the present
lubricating oils will typically be present from 1 to 50 weight, or
more preferably from 5 to 50 percent, or more preferably from 10 to
40 percent, or more preferably from 20 to 30 percent.
Other Additives
[0071] The formulated lubricating oil useful in the present
disclosure may additionally contain one or more of the other
commonly used lubricating oil performance additives including but
not limited to dispersants, other detergents, corrosion inhibitors,
rust inhibitors, metal deactivators, other anti-wear agents and/or
extreme pressure additives, anti-seizure agents, wax modifiers,
viscosity index improvers, viscosity modifiers, fluid-loss
additives, seal compatibility agents, other friction modifiers,
lubricity agents, anti-staining agents, chromophoric agents,
defoamants, demulsifiers, emulsifiers, densifiers, wetting agents,
gelling agents, tackiness agents, colorants, and others. For a
review of many commonly used additives, see Klamann in Lubricants
and Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN
0-89573-177-0. Reference is also made to "Lubricant Additives
Chemistry and Applications" edited by Leslie R. Rudnick, Marcel
Dekker, Inc. New York, 2003 ISBN: 0-8247-0857-1.
[0072] All of the additives described below can be used alone or in
combination. The total treat rates for the additives can range from
1 to 30 percent, or more preferably from 2 to 25 percent, or more
preferably from 3 to 20 percent, or more preferably from 4 to 15
percent, or more preferably from 5 to 10 percent. Particularly
preferred compositions have additive levels between 15 and 20
percent.
[0073] The types and quantities of performance additives used in
combination with the instant disclosure in lubricant compositions
are not limited by the examples shown herein as illustrations.
Viscosity Modifiers
[0074] Viscosity modifiers (also known as viscosity index
improvers--VI improvers--and viscosity improvers) can be included
in the lubricant compositions of this disclosure.
[0075] Viscosity modifiers provide lubricants with high and low
temperature operability. These additives impart shear stability at
elevated temperatures and acceptable viscosity at low
temperatures.
[0076] Suitable viscosity modifiers include high molecular weight
hydrocarbons, polyesters and viscosity modifier dispersants that
function as both a viscosity modifier and a dispersant. Typical
molecular weights of these polymers are between about 10,000 to
1,500,000, more typically about 20,000 to 1,200,000, and even more
typically between about 50,000 and 1,000,000.
[0077] Examples of suitable viscosity modifiers are linear or
star-shaped polymers and copolymers of methacrylate, butadiene,
olefins, or alkylated styrenes. Polyisobutylene is a commonly used
viscosity modifier. Another suitable viscosity modifier is
polymethacrylate (copolymers of various chain length alkyl
methacrylates, for example), some formulations of which also serve
as pour point depressants. Other suitable viscosity modifiers
include copolymers of ethylene and propylene, hydrogenated block
copolymers of styrene and isoprene, and polyacrylates (copolymers
of various chain length acrylates, for example). Specific examples
include styrene-isoprene or styrene-butadiene based polymers of
50,000 to 200,000 molecular weight.
[0078] Olefin copolymers are commercially available from Chevron
Oronite Company LLC under the trade designation "PARATONE.RTM."
(such as "PARATONE.RTM. 8921" and "PARATONE.RTM. 8941"); from Afton
Chemical Corporation under the trade designation "HiTEC.RTM." (such
as "HiTEC.RTM. 5850B"; and from The Lubrizol Corporation under the
trade designation "Lubrizol.RTM. 7067C". Hydrogenated polyisoprene
star polymers are commercially available from Infineum
International Limited, e.g., under the trade designation "SV200"
and "SV600". Hydrogenated diene-styrene block copolymers are
commercially available from Infineum International Limited, e.g.,
under the trade designation "SV 50".
[0079] The polymethacrylate or polyacrylate polymers can be linear
polymers which are available from Evnoik Industries under the trade
designation "Viscoplex.RTM." (e.g., Viscoplex 6-954) or star
polymers which are available from Lubrizol Corporation under the
trade designation Asteric.TM. (e.g., Lubrizol 87708 and Lubrizol
87725).
[0080] Illustrative vinyl aromatic-containing polymers useful in
this disclosure may be derived predominantly from vinyl aromatic
hydrocarbon monomer. Illustrative vinyl aromatic-containing
copolymers useful in this disclosure may be represented by the
following general formula:
A-B
wherein A is a polymeric block derived predominantly from vinyl
aromatic hydrocarbon monomer, and B is a polymeric block derived
predominantly from conjugated diene monomer.
[0081] The vinyl aromatic-containing polymers or copolymers useful
in this disclosure have a weight average molecular weight greater
than about 80,000, and a number average molecular weight greater
than about 40,000; preferably a weight average molecular weight
greater than about 90,000, and a number average molecular weight
greater than about 75,000; and more preferably a weight average
molecular weight greater than about 100,000 and less than
1,000,000, and a number average molecular weight greater than about
100,000 and less than 1,000,000. The vinyl aromatic-containing
polymers or copolymers have an amount of vinyl aromatic content
greater than about 10% by weight, or greater than about 20% by
weight, or greater than about 30% by weight, of the vinyl
aromatic-containing polymer or copolymer. The vinyl
aromatic-containing polymers or copolymers have an amount of vinyl
aromatic content preferably between about 10% and about 50% by
weight, more preferably between about 15% and about 40% by weight,
and even more preferably between about 20% and about 35% by weight,
of the vinyl aromatic-containing polymer or copolymer.
[0082] In an embodiment of this disclosure, the viscosity modifiers
may be used in an amount of less than about 2.0 weight percent,
preferably less than about 1.0 weight percent, and more preferably
less than about 0.5 weight percent, based on the total weight of
the formulated oil or lubricating engine oil. Viscosity modifiers
are typically added as concentrates, in large amounts of diluent
oil.
[0083] In another embodiment of this disclosure, the viscosity
modifiers may be used in an amount of from 0.05 to about 2.0 weight
percent, preferably 0.15 to about 1.0 weight percent, and more
preferably 0.25 to about 0.5 weight percent, based on the total
weight of the formulated oil or lubricating engine oil. Or the
viscosity modifiers may be used in an amount (total solid polymer
content) of from 0.5 to about 2.0 weight percent, preferably 0.8 to
about 1.5 weight percent, and more preferably 1.0 to about 1.3
weight percent, based on the total weight of the formulated oil or
lubricating engine oil.
[0084] As used herein, the viscosity modifier concentrations are
given on an "as delivered" basis. Typically, the active polymer is
delivered with a diluent oil. The "as delivered" viscosity modifier
typically contains from 20 weight percent to 75 weight percent of
an active polymer for polymethacrylate or polyacrylate polymers, or
from 8 weight percent to 20 weight percent of an active polymer for
olefin copolymers, hydrogenated polyisoprene star polymers, or
hydrogenated diene-styrene block copolymers, in the "as delivered"
polymer concentrate.
Antioxidants
[0085] Typical anti-oxidant include phenolic anti-oxidants, aminic
anti-oxidants and oil-soluble copper complexes.
[0086] The phenolic antioxidants include sulfurized and
non-sulfurized phenolic antioxidants. The terms "phenolic type" or
"phenolic antioxidant" used herein includes compounds having one or
more than one hydroxyl group bound to an aromatic ring which may
itself be mononuclear, e.g., benzyl, or poly-nuclear, e.g.,
naphthyl and Spiro aromatic compounds. Thus "phenol type" includes
phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc.,
as well as alkyl or alkenyl and sulfurized alkyl or alkenyl
derivatives thereof, and bisphenol type compounds including such
bi-phenol compounds linked by alkylene bridges sulfuric bridges or
oxygen bridges. Alkyl phenols include mono- and poly-alkyl or
alkenyl phenols, the alkyl or alkenyl group containing from about
3-100 carbons, preferably 4 to 50 carbons and sulfurized
derivatives thereof, the number of alkyl or alkenyl groups present
in the aromatic ring ranging from 1 to up to the available
unsatisfied valences of the aromatic ring remaining after counting
the number of hydroxyl groups bound to the aromatic ring.
[0087] Generally, therefore, the phenolic anti-oxidant may be
represented by the general formula:
(R).sub.x--Ar--(OH).sub.y
where Ar is selected from the group consisting of:
##STR00010##
wherein R is a C.sub.3-C.sub.100 alkyl or alkenyl group, a sulfur
substituted alkyl or alkenyl group, preferably a C.sub.4-C.sub.50
alkyl or alkenyl group or sulfur substituted alkyl or alkenyl
group, more preferably C.sub.3-C.sub.100 alkyl or sulfur
substituted alkyl group, most preferably a C.sub.4-C.sub.50 alkyl
group, R.sup.G is a C.sub.1-C.sub.100 alkylene or sulfur
substituted alkylene group, preferably a C.sub.2-C.sub.50 alkylene
or sulfur substituted alkylene group, more preferably a
C.sub.2-C.sub.2 alkylene or sulfur substituted alkylene group, y is
at least 1 to up to the available valences of Ar, x ranges from 0
to up to the available valances of Ar-y, z ranges from 1 to 10, n
ranges from 0 to 20, and m is 0 to 4 and p is 0 or 1, preferably y
ranges from 1 to 3, x ranges from 0 to 3, z ranges from 1 to 4 and
n ranges from 0 to 5, and p is 0.
[0088] Preferred phenolic anti-oxidant compounds are the hindered
phenolics and phenolic esters which contain a sterically hindered
hydroxyl group, and these include those derivatives of dihydroxy
aryl compounds in which the hydroxyl groups are in the o- or
p-position to each other. Typical phenolic anti-oxidants include
the hindered phenols substituted with C.sub.1+ alkyl groups and the
alkylene coupled derivatives of these hindered phenols. Examples of
phenolic materials of this type 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; 2-methyl-6-t-butyl-4-dodecyl
phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl
phenol; and 2,6-di-t-butyl 4 alkoxy phenol; and
##STR00011##
[0089] Phenolic type anti-oxidants are well known in the
lubricating industry and commercial examples such as Ethanox.RTM.
4710, Irganox.RTM. 1076, Irganox.RTM. L1035, Irganox.RTM. 1010,
Irganox.RTM. L109, Irganox.RTM. L118, Irganox.RTM. L135 and the
like are familiar to those skilled in the art. The above is
presented only by way of exemplification, not limitation on the
type of phenolic anti-oxidants which can be used.
[0090] The phenolic anti-oxidant can be employed in an amount in
the range of about 0.1 to 5 wt %, preferably about 0.5 to 3 wt %,
more preferably 1 to 3 wt % on an active ingredient basis.
[0091] Aromatic amine anti-oxidants include phenyl-a-naphthyl amine
which is described by the following molecular structure:
##STR00012##
wherein R.sup.z is hydrogen or a C.sub.1 to C.sub.14 linear or
C.sub.3 to C.sub.14 branched alkyl group, preferably C.sub.1 to
C.sub.10 linear or C.sub.3 to C.sub.10 branched alkyl group, more
preferably linear or branched C.sub.6 to C.sub.8 and n is an
integer ranging from 1 to 5 preferably 1. A particular example is
Irganox L06.
[0092] Other aromatic amine anti-oxidants include other alkylated
and non-alkylated aromatic amines such as aromatic monoamines of
the formula R.sup.8R.sup.9R.sup.10N where R.sup.8 is an aliphatic,
aromatic or substituted aromatic group, R.sup.9 is an aromatic or a
substituted aromatic group, and R.sup.10 is H, alkyl, aryl or
R.sup.11S(O)xR.sup.12 where R.sup.11 is an alkylene, alkenylene, or
aralkylene group, R.sup.12 is a higher alkyl group, or an alkenyl,
aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic group
R.sup.8 may contain from 1 to about 20 carbon atoms, and preferably
contains from about 6 to 12 carbon atoms. The aliphatic group is a
saturated aliphatic group. Preferably, both R.sup.8 and R.sup.9 are
aromatic or substituted aromatic groups, and the aromatic group may
be a fused ring aromatic group such as naphthyl. Aromatic groups
R.sup.8 and R.sup.9 may be joined together with other groups such
as S.
[0093] Typical aromatic amines anti-oxidants have alkyl substituent
groups of at least about 6 carbon atoms. Examples of aliphatic
groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally,
the aliphatic groups will not contain more than about 14 carbon
atoms. The general types of such other additional amine
anti-oxidants which may be present include diphenylamines,
phenothiazines, imidodibenzyls and diphenyl phenylene diamines.
Mixtures of two or more of such other additional aromatic amines
may also be present. Polymeric amine antioxidants can also be
used.
[0094] Aromatic amines anti-oxidants can be employed in an amount
in the range of about 0.1 to 5 wt %, preferably about 0.5 to 3 wt
%, more preferably 1 to 3 wt % on an active ingredient basis.
[0095] Another class of anti-oxidant used in lubricating oil
compositions and which may also be present are oil-soluble copper
compounds. Any oil-soluble suitable copper compound may be blended
into the lubricating oil. Examples of suitable copper antioxidants
include copper dihydrocarbyl thio- or dithio-phosphates and copper
salts of carboxylic acid (naturally occurring or synthetic). Other
suitable copper salts include copper dithiacarbamates, sulphonates,
phenates, and acetylacetonates. Basic, neutral, or acidic copper
Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or
anhydrides are known to be particularly useful.
[0096] Such antioxidants may be used individually or as mixtures of
one or more types of antioxidants, the total amount employed being
an amount of about 0.50 to 5 wt %, preferably about 0.75 to 3 wt %
(on an as-received basis).
Detergents
[0097] Illustrative detergents useful in this disclosure include,
for example, alkali metal detergents, alkaline earth metal
detergents, or mixtures of one or more alkali metal detergents and
one or more alkaline earth metal detergents. Oils formulated with
low concentrations of detergents and/or low ash detergents can be
preferred as low ash, low metals, low phosphorus oils. 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.
[0098] Salts that contain a substantially stochiometric amount of
the metal are described as neutral salts and have a total base
number (TBN, as measured by ASTM D2896) of from 0 to 80. Many
compositions are overbased, containing large amounts of a metal
base that is achieved by reacting an excess of a metal compound (a
metal hydroxide or oxide, for example) with an acidic gas (such as
carbon dioxide). Useful detergents can be neutral, mildly
overbased, or highly overbased. These detergents can be used in
mixtures of neutral, overbased, highly overbased calcium
salicylate, sulfonates, phenates and/or magnesium salicylate,
sulfonates, phenates. The TBN ranges can vary from low, medium to
high TBN products, including as low as 0 to as high as 600.
Mixtures of low, medium, high TBN can be used, along with mixtures
of calcium and magnesium metal based detergents, and including
sulfonates, phenates, salicylates, and carboxylates. A detergent
mixture with a metal ratio of 1, in conjunction of a detergent with
a metal ratio of 2, and as high as a detergent with a metal ratio
of 5, can be used. Borated detergents can also be used.
[0099] Alkaline earth phenates are another useful class of
detergent. These detergents can be made by reacting alkaline earth
metal hydroxide or oxide (CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2,
for example) with an alkyl phenol or sulfurized alkylphenol. Useful
alkyl groups include straight chain or branched C1-C30 alkyl
groups, preferably, C4-C20 or mixtures thereof. Examples of
suitable phenols include isobutylphenol, 2-ethylhexylphenol,
nonylphenol, dodecyl phenol, and the like. It should be noted that
starting alkylphenols may contain more than one alkyl substituent
that are each independently straight chain or branched and can be
used from 0.5 to 6 weight percent. When a non-sulfurized
alkylphenol is used, the sulfurized product may be obtained by
methods well known in the art. These methods include heating a
mixture of alkylphenol and sulfurizing agent (including elemental
sulfur, sulfur halides such as sulfur dichloride, and the like) and
then reacting the sulfurized phenol with an alkaline earth metal
base.
[0100] Metal salts of carboxylic acids are also useful as
detergents. These carboxylic acid detergents may be prepared by
reacting a basic metal compound with at least one carboxylic acid
and removing free water from the reaction product. These compounds
may be overbased to produce the desired TBN level. Detergents made
from salicylic acid are one preferred class of detergents derived
from carboxylic acids. Useful salicylates include long chain alkyl
salicylates. One useful family of compositions is of the
formula
##STR00013##
where R is an alkyl group having 1 to about 30 carbon atoms, n is
an integer from 1 to 4, and M is an alkaline earth metal. Preferred
R groups are alkyl chains of at least C11, preferably C13 or
greater. R may be optionally substituted with substituents that do
not interfere with the detergent's function. M is preferably,
calcium, magnesium, or barium. More preferably, M is calcium or
magnesium.
[0101] Hydrocarbyl-substituted salicylic acids may be prepared from
phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). The
metal salts of the hydrocarbyl-substituted salicylic acids may be
prepared by double decomposition of a metal salt in a polar solvent
such as water or alcohol.
[0102] Alkaline earth metal phosphates are also used as detergents
and are known in the art.
[0103] Detergents may be simple detergents or what is known as
hybrid or complex detergents. The latter detergents can provide the
properties of two detergents without the need to blend separate
materials. See U.S. Pat. No. 6,034,039.
[0104] Preferred detergents include calcium phenates, calcium
sulfonates, calcium salicylates, magnesium phenates, magnesium
sulfonates, magnesium salicylates and other related components
(including borated detergents), and mixtures thereof. Preferred
mixtures of detergents include magnesium sulfonate and calcium
salicylate, magnesium sulfonate and calcium sulfonate, magnesium
sulfonate and calcium phenate, calcium phenate and calcium
salicylate, calcium phenate and calcium sulfonate, calcium phenate
and magnesium salicylate, calcium phenate and magnesium
phenate.
[0105] The lubricating oils of this disclosure exhibit desired
properties, e.g., wear control, deposit control and fuel
efficiency, in the presence or absence of a detergent, in
particular, the presence or absence of a salicylate detergent or a
sulfonate detergent.
[0106] The detergent concentration in the lubricating oils of this
disclosure can range from about 0.5 to about 20 weight percent or
more, preferably about 0.6 to 5.0 weight percent, and more
preferably from about 0.8 weight percent to about 4.0 weight
percent, based on the total weight of the lubricating oil.
[0107] As used herein, the detergent concentrations are given on an
"as delivered" basis. Typically, the active detergent is delivered
with a process oil. The "as delivered" detergent typically contains
from about 20 weight percent to about 100 weight percent, or from
about 40 weight percent to about 60 weight percent, of active
detergent in the "as delivered" detergent product.
Dispersants
[0108] During engine operation, oil-insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposition on metal surfaces. Dispersants
may be ashless or ash-forming in nature. Preferably, the dispersant
is ashless. So called ashless dispersants are organic materials
that form substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents
discussed above form ash upon combustion.
[0109] Suitable dispersants typically contain a polar group
attached to a relatively high molecular weight hydrocarbon chain.
The polar group typically contains at least one element of
nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain
50 to 400 carbon atoms.
[0110] A particularly useful class of dispersants are the
alkenylsuccinic derivatives, typically produced by the reaction of
a long chain substituted alkenyl succinic compound, usually 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 normally a
polyisobutylene group. Polyisobutylene group with high terminal
vinylic content can be preferred. Many examples of this type of
dispersant are well known commercially and in the literature.
Exemplary patents describing such dispersants are U.S. Pat. Nos.
3,172,892; 3,219,666; 3,316,177 and 4,234,435. Other types of
dispersants are described in U.S. Pat. Nos. 3,036,003; and
5,705,458.
[0111] Hydrocarbyl-substituted succinic acid compounds are popular
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound preferably having at
least 50 carbon atoms in the hydrocarbon substituent, with at least
one equivalent of an alkylene amine are particularly useful.
[0112] Succinimides are formed by the condensation reaction between
alkenyl succinic anhydrides and amines. Molar ratios can vary
depending on the amine or polyamine. For example, the molar ratio
of alkenyl succinic anhydride to TEPA can vary from about 1:1 to
about 5:1 or more.
[0113] 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. For
example, the condensation product of an alkenyl succinic anhydride
and pentaerythritol is a useful dispersant.
[0114] Succinate ester amides are formed by condensation reaction
between alkenyl succinic anhydrides and alkanol amines. For
example, suitable alkanol amines include ethoxylated
polyalkylpolyamines, propoxylated polyalkylpolyamines and
polyalkenylpolyamines such as polyethylene polyamines. One example
is propoxylated hexamethylenediamine.
[0115] The molecular weight of the alkenyl succinic anhydrides will
typically range between 400 and 5,000 with preferred ranges between
800 and 2,500. The above products can be post-reacted with various
reagents such as sulfur, oxygen, formaldehyde, carboxylic acids
such as oleic acid, and boron compounds such as 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.
[0116] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. Process aids and catalysts,
such as oleic acid and sulfonic acids, can also be part of the
reaction mixture. Molecular weights of the alkylphenols range from
800 to 2,500. Mannich base dispersants can also be borated and
mixtures of Mannich base dispersants can be used.
[0117] Typical high molecular weight aliphatic acid modified
Mannich condensation products can be prepared from high molecular
weight alkyl-substituted hydroxyaromatics or HN(R)2
group-containing reactants.
[0118] Examples of high molecular weight alkyl-substituted
hydroxyaromatic compounds are polypropylphenol, polybutylphenol,
and other polyalkylphenols. These polyalkylphenols can be obtained
by the alkylation, in the presence of an alkylating catalyst, such
as BF3, 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.
[0119] Examples of HN(R).sub.2 group-containing reactants are
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 are well known and 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.
[0120] Examples of alkylene polyamine 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, mentioned
before, 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-, pentapropylene 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.
[0121] Aldehyde reactants useful in the preparation of the high
molecular products useful in this disclosure include the aliphatic
aldehydes such as formaldehyde (also as paraformaldehyde and
formalin), acetaldehyde and aldol (.beta.-hydroxybutyraldehyde).
Formaldehyde or a formaldehyde-yielding reactant is preferred.
[0122] Preferred dispersants include borated and non-borated
succinimides, including those derivatives from mono-succinimides,
bis-succinimides, and/or mixtures of mono- and bis-succinimides,
wherein the hydrocarbyl succinimide is derived from a
hydrocarbylene group such as polyisobutylene having a Mn of from
about 500 to about 5000 or a mixture of such hydrocarbylene groups.
Other preferred dispersants include succinic acid-esters and
amides, alkylphenol-polyamine-coupled Mannich adducts, their
borates and capped derivatives, such as, polycyclic carbonates, and
other related components. Such additives may be used in an amount
of about 0.1 to 20 wt %, preferably about 0.1 to 8 wt %, more
preferably about 1 to 6 wt % (on an as-received basis or 0-10 wt %
on an active ingredient basis) based on the weight of the total
lubricant.
Pour Point Depressants
[0123] Conventional pour point depressants (also known as lube oil
flow improvers) may also be present. Pour point depressant may be
added to lower the minimum temperature at which the fluid will flow
or can be poured. Examples of suitable pour point depressants
include alkylated naphthalenes polymethacrylates, polyacrylates,
polyarylamides, condensation products of haloparaffin waxes and
aromatic compounds, vinyl carboxylate polymers, and terpolymers of
dialkylfumarates, vinyl esters of fatty acids and allyl vinyl
ethers. Such additives may be used in amount of about 0.0 to 0.5 wt
%, preferably about 0 to 0.3 wt %, more preferably about 0.001 to
0.1 wt % on an as-received basis.
Corrosion Inhibitors/Metal Deactivators
[0124] Corrosion inhibitors are used to reduce the degradation of
metallic parts that are in contact with the lubricating oil
composition. Suitable corrosion inhibitors include aryl thiazines,
alkyl substituted dimercapto thiodiazoles thiadiazoles and mixtures
thereof. Such additives may be used in an amount of about 0.01 to 5
wt %, preferably about 0.01 to 1.5 wt %, more preferably about 0.01
to 0.2 wt %, still more preferably about 0.01 to 0.1 wt % (on an
as-received basis) based on the total weight of the lubricating oil
composition.
Seal Compatibility Additives
[0125] Seal compatibility agents help to swell elastomeric seals by
causing a chemical reaction in the fluid or physical change in the
elastomer. Suitable seal compatibility agents for lubricating oils
include organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (butylbenzyl phthalate, for example), and polybutenyl
succinic anhydride and sulfolane-type seal swell agents such as
Lubrizol 730-type seal swell additives. Such additives may be used
in an amount of about 0.01 to 3 wt %, preferably about 0.01 to 2 wt
% on an as-received basis.
Anti-Foam Agents
[0126] Anti-foam agents may advantageously be added to lubricant
compositions. These agents retard the formation of stable foams.
Silicones and organic polymers are typical anti-foam agents. For
example, polysiloxanes, such as silicon oil or polydimethyl
siloxane, provide antifoam properties. Anti-foam agents are
commercially available and may be used in conventional minor
amounts along with other additives such as demulsifiers; usually
the amount of these additives combined is less than 1 percent,
preferably 0.001 to about 0.5 wt %, more preferably about 0.001 to
about 0.2 wt %, still more preferably about 0.0001 to 0.15 wt % (on
an as-received basis) based on the total weight of the lubricating
oil composition.
Inhibitors and Antirust Additives
[0127] Anti-rust additives (or corrosion inhibitors) are additives
that protect lubricated metal surfaces against chemical attack by
water or other contaminants. One type of anti-rust additive is a
polar compound that wets the metal surface preferentially,
protecting it with a film of oil. Another type of anti-rust
additive absorbs water by incorporating it in a water-in-oil
emulsion so that only the oil touches the surface. Yet another type
of anti-rust additive chemically adheres to the metal to produce a
non-reactive surface. Examples of suitable additives include zinc
dithiophosphates, metal phenolates, basic metal sulfonates, fatty
acids and amines. Such additives may be used in an amount of about
0.01 to 5 wt %, preferably about 0.01 to 1.5 wt % on an as-received
basis.
[0128] ZDDP anti-wear additives are essential components of the
present disclosure. ZDDP derived from C8 to C18 primary or
secondary alcohols and preferably derived from C4, C5, and/or C7
primary or secondary alcohols and mixtures thereof are often
preferred. In some applications, low phosphorus ZDDP additives with
<0.10% by weight phosphorus, leading to about from 0.02% to
0.08% phosphorus in finished oils can be preferred. In addition to
ZDDP, other anti-wear additives can be present, including zinc
dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum
dithiocarbamates, other organo molybdenum-nitrogen complexes,
sulfurized olefins, etc.
[0129] The term "organo molybdenum-nitrogen complexes" embraces the
organo molybdenum-nitrogen complexes described in U.S. Pat. No.
4,889,647. The complexes are reaction products of a fatty oil,
dithanolamine and a molybdenum source. Specific chemical structures
have not been assigned to the complexes. U.S. Pat. No. 4,889,647
reports an infrared spectrum for a typical reaction product of that
disclosure; the spectrum identifies an ester carbonyl band at 1740
cm.sup.-1 and an amide carbonyl band at 1620 cm.sup.-1. The fatty
oils are glyceryl esters of higher fatty acids containing at least
12 carbon atoms up to 22 carbon atoms or more. The molybdenum
source is an oxygen-containing compound such as ammonium
molybdates, molybdenum oxides and mixtures.
[0130] Other organo molybdenum complexes which can be used in the
present disclosure are tri-nuclear molybdenum-sulfur compounds
described in EP 1 040 115 and WO 99/31113 and the molybdenum
complexes described in U.S. Pat. No. 4,978,464.
Performance and Uses
[0131] The lubricant compositions of this disclosure give
advantaged performance in the lubrication of internal combustion
engines, power trains, drivelines, transmissions, gears, gear
trains, gear sets, compressors, pumps, hydraulic systems, bearings,
bushings, turbines, and the like.
[0132] Also, the lubricant compositions of this disclosure give
advantaged friction, wear, and other lubricant performances in the
lubrication of mechanical components, which comprise, for example,
pistons, piston rings, cylinder liners, cylinders, cams, tappets,
lifters, bearings (journal, roller, tapered, needle, ball, and the
like), gears, valves, and the like.
[0133] Further, the lubricant compositions of this disclosure give
advantaged friction, wear, and other lubricant performances under a
range of lubrication contact pressures, from 1 MPas to greater than
10 GPas, preferably greater than 10 MPas, more preferably greater
than 100 MPas, even more preferable greater than 300 MPas. Under
certain circumstances, the instant disclosure gives advantaged wear
and friction performance at greater than 0.5 GPas, often at greater
than 1 GPas, sometimes greater than 2 GPas, under selected
circumstances greater than 5 GPas.
[0134] Yet further, the lubricant compositions of this disclosure
give advantaged friction, wear, and other lubricant performances
when used in combination with lubricated surfaces comprising:
metals, metal alloys, non-metals, non-metal alloys, mixed
carbon-metal composites and alloys, mixed carbon-nonmetal
composites and alloys, ferrous metals, ferrous composites and
alloys, non-ferrous metals, non-ferrous composites and alloys,
titanium, titanium composites and alloys, aluminum, aluminum
composites and alloys, magnesium, magnesium composites and alloys,
ion-implanted metals and alloys, plasma modified surfaces; surface
modified materials; coatings; mono-layer, multi-layer, and gradient
layered coatings; honed surfaces; polished surfaces; etched
surfaces; textured surfaces; micro and nano structures on textured
surfaces; super-finished surfaces; diamond-like carbon (DLC), DLC
with high-hydrogen content, DLC with moderate hydrogen content, DLC
with low-hydrogen content, DLC with zero hydrogen content, DLC
composites, DLC-metal compositions and composites, DLC-nonmetal
compositions and composites; glasses, metallic glasses; ceramics,
cermets, ceramic oxides, ceramic nitrides, FeN, CrN, ceramic
carbides, mixed ceramic compositions, and the like; polymers,
plastics, thermoplastic polymers, engineered polymers, polymer
blends, polymer alloys, polymer composites; elastomers; materials
compositions and composites containing dry lubricants, comprising
for example graphite, carbon, molybdenum, molybdenum disulfide,
polytetrafluoroethylene, polyperfluoropropylene,
polyperfluoroalkylethers, and the like.
[0135] The viscometric properties of the lubricants of this
disclosure can be measured according to standard practices. A low
viscosity can be advantageous for lubricants in modern equipment. A
low high temperature high shear (HTHS) viscosity, in accordance
with ASTM D4683, can indicate performance of a lubricant in a
modern engine. In particular, the lubricants of this disclosure can
have an HTHS of less than 2.0 cP, or more preferably less than 1.9
cP, or more preferably less than 1.8 cP, or more preferably less
than 1.7 cP.
[0136] The lubricants of this disclosure can have lower volatility,
as determined by the Noack volatility test ASTM D5800, or as
predicted by a TGA test that simulates the Noack volatility. In
particular, the lubricants of this disclosure can have a Noack
between 1% and 50%, or more preferably between 10% and 50%, or more
preferably between 15% and 40%, or more preferably between 20% and
30%. Particularly preferred compositions have a Noack between 15%
and 30%.
[0137] The lubricants of this disclosure can have lower deposition
tendency, as determined by the TEOST 33C deposition test ASTM
D6335. In particular, the lubricants of this disclosure can have a
TEOST 33C of less than 30 mg, or more preferably less than 20 mg,
or more preferably less than 15 mg.
[0138] The lubricants of this disclosure can have reduced traction
as determined by the MTM (Mini Traction Machine) traction test.
Traction is most easily assessed by comparison to a reference
fluid, in this case a suitable reference fluid is an engine oil
formulated with commercial diioctyl adipate ester such as
Esterex.TM. A32. Accordingly, the lubricants of this disclosure can
have an MTM traction reduction of 5% versus a reference, or more
preferably a reduction of 10% versus a reference, or more
preferably a reduction of 20% versus a reference, or more
preferably a reduction of 30% versus a reference, or more
preferably a reduction of 40% versus a reference.
[0139] In the above detailed description, the specific embodiments
of this disclosure have been described in connection with its
preferred embodiments. However, to the extent that the above
description is specific to a particular embodiment or a particular
use of this disclosure, this is intended to be illustrative only
and merely provides a concise description of the exemplary
embodiments. Accordingly, the disclosure is not limited to the
specific embodiments described above, but rather, the disclosure
includes all alternatives, modifications, and equivalents falling
within the true scope of the appended claims. Various modifications
and variations of this disclosure will be obvious to a worker
skilled in the art and it is to be understood that such
modifications and variations are to be included within the purview
of this application and the spirit and scope of the claims.
EXAMPLES
Example 1
Preparation of 2-butyloctyl 4-butyl benzoate
[0140] To a 3-neck 1000-ml round-bottomed flask with a dean-stark
apparatus was added and mixed 2-butyloctanol (10.46 g, 0.0561 mol,
MW: 186.54), 4-butyllbenzoic acid (5.0 g 0.0281 mol, MW: 178.23)
and p-toluenesulfonic acid monohydride (PTSA) (1.1 g, 0.00562 mol,
MW: 190.22) and also mixed with 75 ml toluene. The resulting
mixture was heated at reflux for overnight (18 hours). In 18 hours,
about 3 ml water was collected in the dean-stark trap. Toluene was
removed by simple distillation at 75.degree. C. under vacuum and
excess of 2-butyloctanol was distilled with air bath oven at
180.degree. C. under high vacuum. The product was extracted in
hexane and followed by flash chromatography. The hexane layer was
removed by roto-vap at 50.degree. C. under vacuum. The isolated
product was characterized by IR. Yields: 6.5 g (67%). IR: 2956,
2928, 1719, 1611, 1466, 1415, 1378, 1309, 1271, 1176, 1107, 1020,
760.
##STR00014##
Example 2
Preparation of 2-ethylhexyl 4-heptylbenzoate
[0141] To a 3-neck 1000-ml round-bottomed flask with a dean-stark
apparatus was added and mixed 2-ethylhexanol (8.34 g, 0.0640 mol,
MW: 186.54), 4-heptylbenzoic acid (5.0 g 0.0213 mol, MW: 234.34)
and p-toluenesulfonic acid monohydride (PTSA) (0.812 g, 0.00427
mol, MW: 190.22) and also mixed with 75 ml toluene. The resulting
mixture was heated at reflux for overnight (18 hours). In 18 hours,
about 3 ml water was collected in the dean-stark trap. Toluene was
removed by simple distillation at 75.degree. C. under vacuum and
excess of 2-ethylhexanol was distilled with air bath oven at
180.degree. C. under high vacuum. The product was extracted in
hexane and followed by flash chromatography. The hexane layer was
removed by roto-vap at 50.degree. C. under vacuum. The isolated
product was characterized by 1HNMR. Yields: 5.5 g (79%). .sup.1H
NMR (CDCl.sub.3): .delta. 7.97.21 (m, 4H, phenyl ring), 4.20 (d,
2H, O.dbd.C--CH.sub.2--), 2.64 (--CH2), 1.71-1.33 (m, 19H,
--CH.sub.2--), 0.95-0.86 (m, 9H, CH.sub.3).
##STR00015##
Example 3
Preparation of butyloctyl 4-cyano benzoate
[0142] To a 3-neck 1000-ml round-bottomed flask with a dean-stark
apparatus was added and mixed 2-butyloctanol (12.66 g, 0.0680 mol,
MW: 186.34), 4-nitrilebenzoic acid (5.0 g 0.0340 mol, MW: 147.13)
and p-toluenesulfonic acid monohydride (PTSA) (1.29 g, 0.0068 mol,
MW: 190.22) and also mixed with 75 ml toluene. The resulting
mixture was heated at reflux for overnight (18 h hours). In 18
hours, about 3-4 ml of water was collected in the dean-stark trap.
Toluene was removed by simple distillation at 75.degree. C. under
vacuum and excess of 2-butyloctanol was distilled with air bath
oven at 200.degree. C. under high vacuum. The product was extracted
in hexane and followed by flash chromatography. The hexane layer
was removed by roto-vap at 50.degree. C. under vacuum. The isolated
product was characterized by .sup.1HNMR. Yields: 10 g (72%).
.sup.1H NMR (CDCl.sub.3): .delta. 8.05-7.68 (m, 4H, phenyl ring),
4.18 (d, 2H, O.dbd.C--CH.sub.2--), 2.37 (--CH--), 1.21 (m, 18H,
--CH.sub.2--), 0.80 (t, 6H, CH.sub.3).
##STR00016##
Example 4
Preparation of 2-hexyldecyl 4-methyl benzoate
[0143] To a 3-neck 1000-ml round-bottomed flask with a dean-stark
apparatus was added and mixed 2-hexyldecan-1-ol (18.70 g, 0.0771
mol, MW: 242.44), 4-methylbenzoic acid (7.0 g 0.0514 mol, MW:
136.15) and p-toluenesulfonic acid monohydride (PTSA) (1.96 g,
0.0103 mol, MW: 190.22) and also mixed with 75 ml toluene. The
resulting mixture was heated at reflux for overnight (18 hours). In
18 hours, about 3-4 ml water was collected in the dean-stark trap.
Toluene was removed by simple distillation at 75.degree. C. under
vacuum and excess of 2-hexyldecan-1-ol was distilled with air bath
oven at 200.degree. C. under high vacuum. The product was extracted
in hexane and followed by flash chromatography. The hexane layer
was removed by roto-vap at 50.degree. C. under vacuum. The isolated
product was characterized by 1HNMR. Yields: 112.80 g (71%). .sup.1H
NMR (CDCl.sub.3): .delta. 7.86-7.16 (m, 4H, phenyl ring), 4.14 (d,
2H, O.dbd.C--CH.sub.2--), 2.31 (--CH3), 1.70-1.19 (m, 25H,
--CH.sub.2--), 0.79 (t, 6H, CH.sub.3).
##STR00017##
Example 5
Preparation of 2-hexyldecyl 3-fluorobenzoate
##STR00018##
[0145] A stirred solution of 3-fluorobenzoic acid (5.0 g, 35.6
mmol) and 2-hexyl-1-decanol (8.6 g, 35.6 mmol) in dry
dichloromethane (50 mL) was cooled to 0.degree. C. Added EDC.HCl
(13.6 g, 71.2 mmol) portion wise followed by DMAP (4.3 g, 35.6
mmol), and the resulting mixture was warmed to room temperature and
was stirred for 16 h. After completion of the reaction (as per
TLC), water (50 mL) was added and the organic phase was separated.
The aqueous phase was washed with dichloromethane (2.times.50 mL),
and the combined organic phase was washed with water (50 mL) and
brine solution (100 mL), dried over sodium sulphate, filtered and
concentrated under reduced pressure. The crude obtained was
purified by Isolera (silica gel 230-400 mesh: 1-2% ethyl acetate in
petroleum ether as eluents) to afford 2-hexyldecyl 3-fluorobenzoate
(target 11) as a colourless liquid (9.3 g, 71.7%). .sup.1H-NMR (400
MHz, CDCl.sub.3): .delta. 7.83-7.86 (m, 1H), 7.71-7.74 (m, 1H),
7.42-7.46 (m, 1H), 7.26-7.29 (m, 1H), 4.24-4.26 (m, 2H) 1.80-1.90
(m, 1H), 1.30-1.40 (m, 24H), 0.88-0.91 (m, 6H). .sup.13C-NMR (100
MHz, CDCl.sub.3): .delta. 165.5, 163.7, 161.3, 132.8, 129.9, 125.2,
119.8, 116.5, 68.1, 37.4, 31.9, 31.8, 31.8, 31.4, 29.9, 29.6, 29.6,
29.5, 29.3, 26.7, 22.7, 22.6, 14.1, 14.1. Mol Formula:
C.sub.23H.sub.37FO.sub.2, cacld mol. weight; 364.55, mass found by
GCMS; 364.2. Purity by GC; 98.5%.
Example 6
Lube Properties
[0146] The lube properties of the products of Examples 1-4
(2-butyloctyl 4-butyl benzoate, 2-ethylhexyl 4-heptylbenzoate,
butyloctyl 4-cyano benzoate, 2-hexyldecyl 4-methyl benzoate) were
evaluated and the data is shown in FIG. 1. The kinematic viscosity
(Kv) of the liquid product was measured using ASTM D445 or D7042,
and reported at temperatures of 100.degree. C. (Kv at 100.degree.
C.) or 40.degree. C. (Kv at 40.degree. C.). The viscosity index
(VI) was measured according to ASTM D2270 using the measured
kinematic viscosities for each product. Noack volatility was
determined by ASTM D5800. These fluids were evaluated as synthetic
base stocks and the results are shown in FIG. 1.
[0147] FIG. 1 clearly shows that the benzoate monoester base stock
examples of this disclosure (Examples 1-4) all have desirable
viscosity-volatility properties The benzoate monoester base stocks
of this disclosure offer a cost advantage relative to other ester
based base stocks.
[0148] FIG. 2 shows the structure (R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, molecular ion) and properties (KV40, KV100) of
the following compound (V) benzoate monoester base stock examples
of this disclosure: 2-hexyldecyl 4-methyl benzoate, 2-hexyldecyl
2-methyl benzoate, 2-hexyldecyl 3-methyl benzoate, 2-hexyldecyl 2,6
dimethyl benzoate, 2-hexyldecyl 2-ethylbenzoate, 2-hexyldecyl
2-methoxybenzoate, 2-hexyldecyl 3-methoxybenzoate, 2-hexyldecyl
4-methoxybenzoate, 2-hexyldecyl 2-fluorobenzoate, 2-hexyldecyl
3-fluorobenzoate, and 2-hexyldecyl 4-fluorobenzoate.
[0149] The benzoate monoesters of the instant disclosure provide
the following non-limiting advantages, low cost, no toxicity issues
and are commercially used in personal care industry. All these
benzoate monoesters fluids of the instant disclosure have low
viscosity and lower volatility. The benzoate monoester fluids can
also be used as PVC plasticizers.
PCT and EP Clauses:
[0150] 1. A composition comprising one or more compounds
represented by the formula selected from the group consisting
of
##STR00019##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
[0151] wherein said composition has a viscosity (K.sub.V100) from 1
cSt to 10 cSt at 100.degree. C. as determined by ASTM D445, a
viscosity index (VI) from -100 to 300 as determined by ASTM D2270,
and a Noack volatility of no greater than 50 percent as determined
by ASTM D5800.
[0152] 2. The composition of clause 1 which has a viscosity
(K.sub.V100) from about 2 cSt to about 8 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about 25 to
about 150 as determined by ASTM D2270, and a Noack volatility of no
greater than 25 percent as determined by ASTM D5800.
[0153] 3. A composition comprising one or more compounds
represented by the formula selected from the group consisting
of
##STR00020##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
[0154] wherein said composition has a viscosity (K.sub.V100) from
about 1 cSt to about 10 cSt at 100.degree. C. as determined by ASTM
D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800; wherein said compound of
formula (I) is produced by a process comprising reacting
2-butyloctanol with 4-butylbenzoic acid, optionally in the presence
of a catalyst and a solvent, under reaction conditions sufficient
to produce the compound of formula (I); or wherein said compound of
formula (II) is produced by a process comprising reacting
2-ethylhexanol with 4-heptylbenzoic acid, optionally in the
presence of a catalyst and a solvent, under reaction conditions
sufficient to produce the compound of formula (II); or wherein said
compound of formula (III) is produced by a process comprising
reacting 2-butyloctanol with 4-nitrilebenzoic acid, optionally in
the presence of a catalyst and a solvent, under reaction conditions
sufficient to produce the compound of formula (III); or wherein
said compound of formula (IV) is produced by a process comprising
reacting 2-hexyldecan-1-ol with 4-methylbenzoic acid, optionally in
the presence of a catalyst and a solvent, under reaction conditions
sufficient to produce the compound of formula (IV).
[0155] 4. The composition of clause 3 which has a viscosity
(K.sub.V100) from about 2 cSt to about 8 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about 25 to
about 150 as determined by ASTM D2270, and a Noack volatility of no
greater than 25 percent as determined by ASTM D5800.
[0156] 5. A lubricating oil base stock comprising one or more
compounds represented by the formula selected from the group
consisting of
##STR00021##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
[0157] wherein said lubricating oil base stock has a viscosity
(K.sub.V100) from about 1 cSt to about 10 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about -100 to
about 300 as determined by ASTM D2270, and a Noack volatility of no
greater than 50 percent as determined by ASTM D5800.
[0158] 6. The lubricating oil base stock of clause 5 which has a
viscosity (K.sub.V100) from about 2 cSt to about 8 cSt at
100.degree. C. as determined by ASTM D445, a viscosity index (VI)
from about 25 to about 150 as determined by ASTM D2270, and a Noack
volatility of no greater than 25 percent as determined by ASTM
D5800.
[0159] 7. The lubricating oil base stock of clauses 5-6 further
comprising one or more of a viscosity improver, antioxidant,
detergent, dispersant, pour point depressant, corrosion inhibitor,
metal deactivator, seal compatibility additive, anti-foam agent,
inhibitor, and anti-rust additive.
[0160] 8. A lubricating oil comprising a lubricating oil base stock
component, and a monoester cobase stock component; wherein said
monoester cobase stock comprises one or more compounds represented
by the formula selected from the group consisting of
##STR00022##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
[0161] wherein said lubricating oil has a viscosity (K.sub.V100)
from about 1 cSt to about 10 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800.
[0162] 9. The lubricating oil of clause 8 wherein the lubricating
oil base stock comprises a Group I, II, III, IV or V base oil
stock.
[0163] 10. The lubricating oil of clauses 8-9 wherein the
lubricating oil base stock comprises a polyalphaolefin (PAO) or
gas-to-liquid (GTL) oil base stock.
[0164] 11. The lubricating oil of clauses 8-10 wherein the
lubricating oil base stock is present in an amount from about 1
weight percent to about 99 weight percent, and the monoester cobase
stock is present in an amount from about 1 weight percent to about
99 weight percent, based on the total weight of the lubricating
oil.
[0165] 12. The lubricating oil of clauses 8-11 which has a
viscosity (K.sub.V100) from about 2 cSt to about 8 cSt at
100.degree. C. as determined by ASTM D445, a viscosity index (VI)
from about 25 to about 150 as determined by ASTM D2270, and a Noack
volatility of no greater than 25 percent as determined by ASTM
D5800.
[0166] 13. The lubricating oil of clauses 8-12 further comprising
one or more of a viscosity improver, antioxidant, detergent,
dispersant, pour point depressant, corrosion inhibitor, metal
deactivator, seal compatibility additive, anti-foam agent,
inhibitor, and anti-rust additive.
[0167] 14. A method for improving one or more of thermal and
oxidative stability, solubility and dispersancy of polar additives,
deposit control and traction control in a lubricating oil
comprising: providing a lubricating oil including a lubricating oil
base stock component, and a monoester cobase stock component;
wherein said monoester cobase stock comprises one or more compounds
represented by the formula selected from the group consisting
of
##STR00023##
wherein R.sub.2 is a H, F, methoxy, methyl or ethyl group; R.sub.3
is a H, F, methoxy or methyl group; R.sub.4 is a H, F methoxy or
methyl group; R.sub.5 is H and R.sub.6 is H or a methyl group
[0168] wherein said lubricating oil has a viscosity (K.sub.V100)
from about 1 cSt to about 10 cSt at 100.degree. C. as determined by
ASTM D445, a viscosity index (VI) from about -100 to about 300 as
determined by ASTM D2270, and a Noack volatility of no greater than
50 percent as determined by ASTM D5800, and using the lubricating
oil in a formulated oil to improve one or more of thermal and
oxidative stability, solubility and dispersancy of polar additives,
deposit control and traction control.
[0169] 15. The method of clause 14 wherein the lubricating oil base
stock comprises a Group I, II, III, IV or V base oil stock.
[0170] 16. The method of clauses 14-15 wherein the lubricating oil
base stock comprises a polyalphaolefin (PAO) or gas-to-liquid (GTL)
oil base stock.
[0171] 17. The method of clauses 14-16 wherein the lubricating oil
base stock is present in an amount from about 1 weight percent to
about 99 weight percent, and the monoester cobase stock is present
in an amount from about 1 weight percent to about 99 weight
percent, based on the total weight of the lubricating oil.
[0172] 18. The method of clauses 14-17 wherein the lubricating oil
has a viscosity (K.sub.V100) from about 2 to about 8 at 100.degree.
C. as determined by ASTM D445, a viscosity index (VI) from about 25
to about 150 as determined by ASTM D2270, and a Noack volatility of
no greater than 25 percent as determined by ASTM D5800.
[0173] 19. The method of clauses 14-18 wherein the lubricating oil
further comprises one or more of a viscosity improver, antioxidant,
detergent, dispersant, pour point depressant, corrosion inhibitor,
metal deactivator, seal compatibility additive, anti-foam agent,
inhibitor, and anti-rust additive.
[0174] 20. A composition comprising one or more compounds
represented by the formula:
##STR00024##
wherein X is a C.sub.1-C.sub.7 alkyl group, a C.sub.1-C.sub.7
alkoxy group, a C.sub.1-C.sub.7 haloalkyl group, a C.sub.1-C.sub.7
haloalkoxy group, a halogen, a cyano group or a nitro group; n is
from 1 to 5; P is from 1 to 12; Q is from 0 to 12; and P+Q is
greater than 4, and wherein the composition has a viscosity
(K.sub.V100) from about 1 cSt to about 10 cSt at 100.degree. C. as
determined by ASTM D445, a viscosity index (VI) from about -100 to
about 300 as determined by ASTM D2270, and a Noack volatility of no
greater than 50 percent as determined by ASTM D5800.
[0175] All patents and patent applications, test procedures (such
as ASTM methods, UL methods, and the like), and other documents
cited herein are fully incorporated by reference to the extent such
disclosure is not inconsistent with this disclosure and for all
jurisdictions in which such incorporation is permitted.
[0176] When numerical lower limits and numerical upper limits are
listed herein, ranges from any lower limit to any upper limit are
contemplated. While the illustrative embodiments of the disclosure
have been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the disclosure. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present disclosure, including all features
which would be treated as equivalents thereof by those skilled in
the art to which the disclosure pertains.
[0177] The present disclosure has been described above with
reference to numerous embodiments and specific examples. Many
variations will suggest themselves to those skilled in this art in
light of the above detailed description. All such obvious
variations are within the full intended scope of the appended
claims.
* * * * *
References