U.S. patent application number 11/810925 was filed with the patent office on 2008-01-24 for high viscosity novel base stock lubricant extreme viscosity blends.
Invention is credited to James T. Carey, Angela S. Galiano-Roth, Heather M. Haigh, Margaret M. Wu.
Application Number | 20080020954 11/810925 |
Document ID | / |
Family ID | 38832074 |
Filed Date | 2008-01-24 |
United States Patent
Application |
20080020954 |
Kind Code |
A1 |
Haigh; Heather M. ; et
al. |
January 24, 2008 |
High viscosity novel base stock lubricant extreme viscosity
blends
Abstract
A lubricant formulation and method of blending a lubricant
formulation is disclosed. The lubricant formulation comprises at
least two base stocks. The first base stock comprises a viscosity
greater than 300 cSt, Kv100.degree. C. and a tight molecular weight
distribution as a function of viscosity. The second base stock
comprises a viscosity less than 100 cSt, Kv100.degree. C. The
lubricant formulation provides favorable properties.
Inventors: |
Haigh; Heather M.;
(Philadelohia, PA) ; Carey; James T.; (Medford,
NJ) ; Galiano-Roth; Angela S.; (Mullica Hill, NJ)
; Wu; Margaret M.; (Skillman, NJ) |
Correspondence
Address: |
ExxonMobil Research and Engineering Company
P.O. Box 900
Annandale
NJ
08801-0900
US
|
Family ID: |
38832074 |
Appl. No.: |
11/810925 |
Filed: |
June 6, 2007 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60811207 |
Jun 6, 2006 |
|
|
|
Current U.S.
Class: |
508/384 ;
508/110 |
Current CPC
Class: |
C10M 2205/143 20130101;
C10M 171/04 20130101; C10M 111/04 20130101; C10N 2030/18 20130101;
C10M 2203/1025 20130101; C10M 2203/065 20130101; C10M 2205/223
20130101; C10N 2040/25 20130101; C10N 2020/011 20200501; C10M
2205/0206 20130101; C10N 2040/04 20130101; C10M 2205/0285 20130101;
C10N 2030/08 20130101; C10M 2207/2825 20130101; C10M 2203/1085
20130101; C10N 2030/68 20200501; C10M 2207/2805 20130101; C10N
2020/02 20130101; C10N 2030/00 20130101; C10N 2030/02 20130101;
C10N 2030/10 20130101; C10N 2020/04 20130101; C10M 2205/163
20130101; C10N 2070/00 20130101; C10M 2205/173 20130101; C10N
2040/08 20130101; C10M 2203/1006 20130101; C10M 2207/2855 20130101;
C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M 2205/0285
20130101; C10M 2205/0285 20130101; C10M 2203/1085 20130101; C10M
2205/0285 20130101; C10M 2205/0265 20130101; C10M 2203/1085
20130101; C10M 2205/0285 20130101; C10M 2203/1006 20130101; C10M
2205/0285 20130101; C10M 2205/0285 20130101; C10M 2205/173
20130101; C10M 2205/0285 20130101; C10M 2205/163 20130101; C10M
2203/1025 20130101; C10N 2020/02 20130101 |
Class at
Publication: |
508/384 ;
508/110 |
International
Class: |
C10M 139/06 20060101
C10M139/06; C10M 159/18 20060101 C10M159/18 |
Claims
1. A lubricating oil, comprising a) at least two base stocks; b) a
first base having a viscosity at least 300 cSt, Kv100.degree. C.
and the first base stock having a molecular weight distribution
(MWD) as a function of viscosity at least 10 percent less than
algorithm MWD=0.2223+1.0232*log(Kv at 100.degree. C. in cSt); c) a
second base stock with a viscosity less than 100 cSt, Kv100.degree.
C.
2. The lubricating oil of claim 1 wherein the viscosity difference
between the first and the second base stocks is greater than 250
cSt, Kv100.degree. C.
3. The lubricating oil of claim 1 wherein the first base stock is a
metallocene catalyzed PAO base stock.
4. The lubricating oil of claim 1 wherein the second base stock is
chosen from the group consisting of GTL base stock, wax derived
base stock, Poly-Alpha-Olefin (PAO), Brightstocks, Brightstocks
with PIB, Group I base stocks, Group II base stocks, Group III base
stocks, Group V base stocks, Group VI base stocks, and any
combination thereof.
5. The lubricating oil of claim 1 further comprising at least one
additive, the additive chosen from the group consisting of
antiwear, antioxidant, defoamant, demulsifier, detergent,
dispersant, metal passivator, friction reducer, rust inhibitor, and
any combination thereof.
6. The lubricating oil of claim 1 further comprising a third base
stock.
7. The lubricating oil of claim 6, wherein the third base stock is
chosen from a group consisting of a PAO with a viscosity of at
least 1.5 cSt, Kv100.degree. C. and no more than 100 cSt,
Kv100.degree. C., a Group V base stock including ester base stock,
alkylated aromatic and any combination thereof.
8. The lubricating oil of claim 6 wherein the first base stock has
a viscosity greater than 400 cSt, Kv100.degree. C.
9. The lubricating oil of claim 7 wherein the third base stock, is
an alkylated naphthalene or alkylated benzene base stocks.
10. The lubricating oil of claim 1 wherein the second base stock
has a viscosity greater than 1.5 and less than 60 cSt,
Kv100.degree. C.
11. The lubricating oil of claim 1 wherein the viscosity difference
between the first base stock and the second base stock is greater
than 400 cSt, Kv100.degree. C.
12. The lubricating oil of claim 1 wherein the first base stock has
a molecular weight distribution less than algorithm:
MWD=0.41667+0.725*log(Kv at 100.degree. C. in cSt).
13. A lubricating oil, comprising a) at least two base stocks; b) a
first base stock comprising a metallocene catalyzed PAO with a
viscosity greater than 300 cSt, Kv100.degree. C.; c) a second base
stock comprising a oil with a viscosity less than 100 cSt,
Kv100.degree. C.
14. The lubricating oil of claim 13 wherein the first base stock is
greater than 250 cSt, Kv100.degree. C.
15. The lubricating oil of claim 13 wherein the first base stock
has a molecular weight distribution (MWD) as a function of
viscosity at least 10 percent less than algorithm
MWD=0.2223+1.0232*log(Kv at 100.degree. C. in cSt).
16. The lubricating oil of claim 13 wherein the second base stock
has a viscosity greater than 1.5 cSt, Kv100.degree. C.
17. The lubricating oil of claim 13 further comprising an alkylated
naphthalene and an additive package.
18. The lubricating oil of claim 13 wherein the first base stock
has a molecular weight distribution less than algorithm:
MWD=0.41667+0.725*log(Kv at 100.degree. C. in cSt).
19. The lubricating oil of claim 13 wherein the second base stock
is is chosen from the group consisting of GTL lubricants, wax
derived lubricants, Poly Alpha Olefin, Brightstocks, Brightstocks
with PIB, Group I base stocks, Group II base stocks, Group III base
stocks, Group V and any combination thereof.
20. The lubricating oil of claim 13 further comprising an additive,
the additive chosen from the group consisting of antiwear,
antioxidant, defoamant, demulsifier, detergent, dispersant, metal
passivator, friction reducer, rust inhibitor, and any combination
thereof.
21. The lubricating oil of claim 13 further comprising at least one
additive chosen to obtain favorable lubricant properties from the
group consisting of micropitting, air release, pour point, low
temperature viscosity, pour point, shear stability, lower oil
operating temperature, energy efficiency and any combination
thereof.
22. The lubricating oil of claim 13 wherein the viscosity
difference between the first base stock and the second base stock
is greater than 300 cSt, Kv100.degree. C.
23. The lubricating oil of claim 13 wherein the viscosity
difference between the first base stock and the second base stock
is greater than 400 cSt, Kv100.degree. C.
24. A method of blending a lubricating oil, comprising, a)
obtaining a first synthetic base stock lubricant the first base
stock having a viscosity greater than 300 cSt, Kv100.degree. C. and
the first bases stock having a molecular weight distribution (MWD)
as a function of viscosity at least 10 percent less than algorithm
MWD=0.2223+1.0232*log(Kv at 100.degree. C. in cSt); b) obtaining a
second synthetic base stock lubricant, the second base stock
lubricant has a viscosity less than 100 cSt, Kv100.degree. C.; c)
blending the first and second base stock lubricant to produce the
lubricating oil.
25. The lubricating oil of claim 24 wherein the viscosity
difference between the first and the second base stocks is greater
than 250 cSt, Kv100.degree. C.
26. The lubricating oil of claim 24 wherein the high viscosity base
stock is a metallocene catalyzed PAO base stock.
27. The lubricating oil of claim 24 wherein the second base stock
is chosen from the group consisting of GTL lubricants, wax derived
lubricants, Poly Alpha Olefin, Brightstocks, Brightstocks with PIB,
group I base stocks, Group II base stocks, Group III base stocks,
Group V and any combination thereof.
28. The lubricating oil of claim 24 further comprising at least one
additive, the additive chosen from the group consisting of
antiwear, antioxidant, defoamant, demulsifier, detergent,
dispersant, metal passivator, friction reducer, rust inhibitor, and
any combination thereof.
29. The lubricating oil of claim 24 further comprising a third base
stock.
30. The lubricating oil of claim 29, wherein the third base stock
is chosen from a group consisting of a PAO with a viscosity of at
least 1.5 cSt, Kv100.degree. C. and no more than 100 cSt,
Kv100.degree. C., Group V base stock, including ester base stock,
alkylated aromatic and any combination thereof.
31. The lubricating oil of claim 24 wherein the first base stock
has a viscosity greater than 300 cSt, Kv100.degree. C.
32. The lubricating oil of claim 24 further comprising at a third
and fourth base stock, the third base stock comprising a PAO having
a viscosity of at least 2 cSt and less than 60 cSt, Kv100.degree.
C., the fourth base stock comprising an alkylated aromatic base
stock.
33. The lubricating oil of claim 24 wherein the second base stock
has a viscosity greater than 1.5 cSt and less than 40 cSt,
Kv100.degree. C.
34. The lubricating oil of claim 24 wherein the viscosity
difference between the first base stock and the second base stock
is greater than 400.
35. The lubricating oil of claim 24 wherein the first base stock
has a molecular weight distribution less than algorithm:
MWD=0.41667+0.725*log(Kv at 100.degree. C. in cSt).
Description
[0001] This application claims benefit of U.S. Ser. No. 60/811,207
filed Jun. 6, 2006.
BACKGROUND
[0002] Oil operating temperature & efficiencies are very
important to the designers, builders, and user of equipment which
employ worm gearing. On a relative basis, a higher percentage
efficiency rating for a lubricant results in more power (torque)
being transmitted through a subject gearbox. Since more power is
being transferred through a piece of equipment using a more
efficient lubricant, less power is being wasted to friction or
heat. It is desirable for lubricant to be optimized for maximum
power throughput and to therefore allow for lower operating
temperatures. Lower operating temperatures in gearboxes give rise
to several benefits which include: lower energy consumption, longer
machine life, and longer seal life. Seal failures are one of the
principle reasons for repair and down-time in rotating equipment. A
decrease of 10 degrees Celsius of operating temperature can double
seal life and therefore decrease overall costs of operation and
ownership.
[0003] A Small Worm Gear Rig measures both dynamic operating
temperature and efficiency of power throughput simultaneously. In
this gear rig, a splash lubricated bronze on steel worm gear set is
the gearbox design employed. The subject worm drive gearbox, 1.75
inch centerline distance, 20:1 reduction ratio, was mounted in an
L-shaped test rig with high precision torque meters on both the
input and output shafts of the gearbox to measure power throughput
efficiency performance based on control of output torque. The
output torque was controlled to 100% of the rated load with a
service factor of 1.0. Also, gearbox sump oil temperature was
carefully monitored during operation using four thermocouples.
National Basic Sensor located at 4921 Carver Avenue in Trevose, Pa.
sells J-type thermocouples that are suitable for this rig test.
[0004] All torque and temperature data was logged every 10 seconds
for a period of 12 hours after thermal stability was attained. The
efficiency was calculated by establishing the ratio of output
torque to input torque. The resulting efficiency and operational
temperatures were compared for experimental blends to that of
reference oils.
[0005] In addition to temperature & efficiency, air entrainment
is another issue in lubricating oils. All lubricating oil systems
contain some air. It can be found in four phases: free air,
dissolved air, entrained air and foam. Free air is trapped in a
system, such as an air pocket in a hydraulic line. Dissolved air is
in solution with the oil and is not visible to the naked eye. Foam
is a collection of closely packed bubbles surrounded by thin films
of oil that collect on the surface of the oil.
[0006] Air entrainment is a small amount of air in the form of
extremely small bubbles (generally less than 1 mm in diameter)
dispersed throughout the bulk of the oil. Agitation of lubricating
oil with air in equipment, such as bearings, couplings, gears,
pumps, and oil return lines, may produce a dispersion of finely
divided air bubbles in the oil. If the residence time in the
reservoir is too short to allow the air bubbles to rise to the oil
surface, a mixture of air and oil will circulate through the
lubricating oil system. This may result in an inability to maintain
oil pressure (particularly with centrifugal pumps), incomplete oil
films in bearings and gears, and poor hydraulic system performance
or failure. Air entrainment is treated differently than foam, and
is most often a completely separate problem. A partial list of
potential effects of air entrainment include: pump cavitation,
spongy, erratic operation of hydraulics, loss of precision control;
vibrations, oil oxidation, component wear due to reduced lubricant
viscosity, equipment shut down when low oil pressure switches trip,
"micro-dieseling" due to ignition of the bubble sheath at the high
temperatures generated by compressed air bubbles, safety problems
in turbines if overspeed devices do not react quickly enough, and
loss of head in centrifugal pumps.
[0007] Antifoamants, including silicone additives help produce
smaller bubbles in the bulk of the oil. In stagnant systems, the
combination of smaller bubbles and greater sheath density can cause
serious air entrainment problems. Turbine oil systems with
quiescent reservoirs of several thousand gallons may have air
entrainment problems with as little as a half a part per million
silicone.
[0008] One widely used method to test air release properties of
petroleum oils is ASTM D3427-03. This test method measures the time
for the entrained air content to fall to the relatively low value
of 0.2% under a standardized set of test conditions and hence
permits the comparison of the ability of oils to separate entrained
air under conditions where a separation time is available. The
significance of this test method has not been fully established.
However, entrained air can cause sponginess and lack of sensitivity
of the control of turbine and hydraulic systems. This test may not
be suitable for ranking oils in applications where residence times
are short and gas contents are high.
[0009] In the ASTM D3427 method, compressed air is blown through
the test oil, which has been heated to a temperature of 25, 50, or
75.degree. C. After the air flow is stopped, the time required for
the air entrained in the oil to reduce in volume to 0.2% is usually
recorded as the air release time.
[0010] Accordingly, there is a need for a lubricant that provides a
consistent favorable operating temperature and power efficiency
along with air release properties using high viscosity base stock
blends. The present invention satisfies this need by providing a
novel combination of base stocks that give the desired
performance.
SUMMARY
[0011] A novel lubricant formulation is disclosed. In one
embodiment the novel lubricant formulation comprises at least two
base stocks The first base stock is a metallocene catalyzed PAO
(poly-alpha-olefins) with a viscosity greater than 300 cSt,
Kv100.degree. C. having a molecular weight distribution (MWD) as a
function of viscosity at least 10 percent less than the algorithm:
MWD=0.2223+1.0232*log(Kv at 100.degree. C. in cSt). The second base
stock is lubricating oil with a viscosity of less than 100 cSt,
Kv100.degree. C.
[0012] In a second embodiment, the novel lubricant formulation
comprises at least two base stocks. A first base stock comprising a
metallocene catalyzed PAO with a viscosity greater than 400 cSt,
Kv100.degree. C. and a second base stock comprising an oil with a
viscosity less than 60 cSt, Kv100.degree. C.
[0013] A method for blending a novel formulation is also disclosed.
The method comprises obtaining a first synthetic base stock
lubricant. The first base stock having a molecular weight
distribution (MWD) as a function of viscosity at least 10 percent
less than the algorithm: MWD=0.2223+1.0232*log(Kv at 100.degree. C.
in cSt). A second base stock lubricant is obtained. The second base
stock lubricant has a viscosity less than 100 cSt, Kv100.degree. C.
The first and second base stock lubricants are mixed to produce the
lubricating oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a graph illustrating the molecular weight
distribution of High viscosities PAO;
[0015] FIG. 2 is a graph illustrating the improved viscosities
losses or improved shear stability as a function of the viscosity
of the high viscosity metallocene catalyzed base stocks.
[0016] FIG. 3 is a graph showing the improved MSWG efficiency of
gear oils formulated with high viscosity metallocene catalyzed PAO
compared to the commercially available prior art PAO.
[0017] FIG. 4 is a graph showing the improved MSWG operating
temperature of gear oils formulated with high viscosity metallocene
catalyzed PAO compared to the commercially available prior art
PAO.
[0018] FIG. 5 is a graph showing the improved air release of gear
oils formulated with high viscosity metallocene catalyzed PAO
compared to the commercially available gear oils.
[0019] FIG. 6 is a graph showing the improved pour point of gear
oils formulated with high viscosity metallocene catalyzed PAO
compared to the commercially available gear oils.
DETAILED DESCRIPTION
[0020] In this patent, unless specified otherwise, all base stock
viscosities are referred to their 100.degree. C. kinematics
viscosity in cSt as measured by ASTD D445 method. The ISO viscosity
classification which is typically cited for industrial lubes of
finished lubricants based on viscosities observed at 40.degree. C.
We have discovered novel combinations of base stocks that provide
unexpected favorable improvements in lubricating properties. In
various embodiments these properties include favorable improvements
in shear stability, air release, pour point, temperature control,
viscosity loss and energy efficiency. In U.S. Provisional
Application No. 60/811,273, we have discovered a novel combination
of base stocks that provides an unexpected increase in aeration
properties, shear stability and energy efficiency. In U.S.
Provisional Application No. 60/811,207, we have discovered the
benefits of using metallocene catalyzed PAO compared to the prior
art PAO.
[0021] In one embodiment, this novel discovery is based on wide
"bi-modal" and "extreme--modal" blends of oil viscosities which are
base stock viscosity differences of at least 200 cSt, preferably at
least 250 cSt, and possibly greater than 500 cSt, respectively
wherein the high viscosity is at least 300 cSt, and the low
viscosity base stock is less than 60 cSt. Kinematic Viscosity is
determined by ASTM D-445 method by measuring the time for a volume
of liquid to flow under gravity through a calibrated glass
capillary viscometer. Viscosity is typically measured in
centistokes (cSt, or mm.sup.2/s) units. The ISO viscosity
classification which is typically cited for industrial lubes of
finished lubricants based on viscosities observed at 40.degree. C.
Base stock oils used to blend finished oils, are generally
described using viscosities observed at 100.degree. C.
[0022] This "bi-modal" blend of viscosities also provides a
temperature benefit by lowering the lubricant temperature in gear
testing by approximately 10.degree. C. This temperature drop would
provide increased efficiency boosts and extended seal life.
[0023] In the past high viscosity base stocks have not been
practical from some applications due to shear stability problems
resulting in viscosity loss in service due to breakdown of
polymeric chains. We have discovered that new base stocks with low
with narrow molecular weight distributions provide excellent shear
stability. This discovery provided the ability to utilize high
viscosity base stocks in what can be described as "dumbbell",
"bi-modal" and "extreme-modal" blends.
[0024] In a preferred embodiment, the new base stocks are produced
according to the method described in U.S. Provisional Application
Nos. 60/650,206. These base stocks are known as metallocene
catalyzed bases stocks and are described in detail below.
Metallocene Base Stocks
[0025] In one embodiment, the metallocene catalyzed PAO (or mPAO)
used for this invention can be a co-polymer made from at least two
alpha-olefins or more, or a homo-polymer made from a single
alpha-olefin feed by a metallocene catalyst system.
[0026] This copolymer mPAO composition is made from at least two
alpha-olefins of C3 to C30 range and having monomers randomly
distributed in the polymers. It is preferred that the average
carbon number is at least 4.1. Advantageously, ethylene and
propylene, if present in the feed, are present in the amount of
less than 50 wt % individually or preferably less than 50 wt %
combined. The copolymers of the invention can be isotactic,
atactic, syndiotactic polymers or any other form of appropriate
tacticity. These copolymers have useful lubricant properties
including excellent VI, pour point, low temperature viscometrics by
themselves or as blend fluid with other lubricants or other
polymers. Furthermore, these copolymers have narrow molecular
weight distributions and excellent lubricating properties.
[0027] In an embodiment, mPAO is made from the mixed feed LAOs
comprising at least two and up to 26 different linear alpha-olefins
selected from C3 to C30 linear alpha-olefins. In a preferred
embodiment, the mixed feed LAO is obtained from an ethylene growth
process using an aluminum catalyst or a metallocene catalyst. The
growth olefins comprise mostly C6 to C18-LAO. LAOs from other
process, such as the SHOP process, can also be used.
[0028] This homo-polymer mPAO composition is made from single
alpha-olefin chosing from C3 to C30 range, preferably C3 to C16,
most preferably C3 to C14 or C3 to C12. The homo-polymers of the
invention can be isotactic, atactic, syndiotactic polymers or any
combination of these tacticity or other form of appropriate
tacticity. Often the tacticity can be carefully tailored by the
polymerization catalyst and polymerization reaction condition
chosen or by the hydrogenation condition chosen. These
homo-polymers have useful lubricant properties including excellent
VI, pour point, low temperature viscometrics by themselves or as
blend fluid with other lubricants or other polymers. Furthermore,
these homo-polymers have narrow molecular weight distributions and
excellent lubricating properties.
[0029] In another embodiment, the alpha-olefin(s) can be chosen
from any component from a conventional LAO production facility or
from refinery. It can be used alone to make homo-polymer or
together with another LAO available from refinery or chemical
plant, including propylene, 1-butene, 1-pentene, and the like, or
with 1-hexene or 1-octene made from dedicated production facility.
In another embodiment, the alpha-olefins can be chosen from the
alpha-olefins produced from Fischer-Trosch synthesis (as reported
in U.S. Pat. No. 5,382,739). For example, C3 to C16-alpha-olefins,
more preferably linear alpha-olefins, are suitable to make
homo-polymers. Other combinations, such as C4 and C14-LAO; C6 and
C16-LAO; C8, C10, C12-LAO; or C8 and C14-LAO; C6, C10, C14-LAO; C4
and C12-LAO, etc. are suitable to make co-polymers.
[0030] The activated metallocene catalyst can be simple
metallocenes, substituted metallocenes or bridged metallocene
catalysts activated or promoted by, for instance, methylaluminoxane
(MAO) or a non-coordinating anion, such as N,N-dimethylanilinium
tetrakis(perfluorophenyl)borate or other equivalent
non-coordinating anion and optionally with co-activators, typically
trialkylaluminum compounds.
[0031] According to the invention, a feed comprising a mixture of
LAOs selected from C3 to C30 LAOs or a single LAO selected from C3
to C16 LAO, is contacted with an activated metallocene catalyst
under oligomerization conditions to provide a liquid product
suitable for use in lubricant components or as functional fluids.
This invention is also directed to a copolymer composition made
from at least two alpha-olefins of C3 to C30 range and having
monomers randomly distributed in the polymers. The phrase "at least
two alpha-olefins" will be understood to mean "at least two
different alpha-olefins" (and similarly "at least three
alpha-olefins" means "at least three different alpha-olefins", and
so forth).
[0032] In preferred embodiments, the average carbon number (defined
hereinbelow) of said at least two alpha-olefins in said feed is at
least 4.1. In another preferred embodiment, the amount of ethylene
and propylene in said feed is less than 50 wt % individually or
preferably less than 50 wt % combined. A still more preferred
embodiment comprises a feed having both of the aforementioned
preferred embodiments, i.e., a feed having an average carbon number
of at least 4.1 and wherein the amount of ethylene and propylene is
less than 50 wt % individually.
[0033] In embodiments, the product obtained is an essentially
random liquid copolymer comprising the at least two alpha-olefins.
By "essentially random" is meant that one of ordinary skill in the
art would consider the products to be random copolymer. Other
characterizations of randomness, some of which are preferred or
more preferred, are provided herein. Likewise the term "liquid"
will be understood by one of ordinary skill in the art, but more
preferred characterizations of the term are provided herein. In
describing the products as "comprising" a certain number of
alpha-olefins (at least two different alpha-olefins), one of
ordinary skill in the art in possession of the present disclosure
would understand that what is being described in the polymerization
(or oligomerization) product incorporating said certain number of
alpha-olefin monomers. In other words, it is the product obtained
by polymerizing or oligomerizing said certain number of
alpha-olefin monomers.
[0034] This improved process employs a catalyst system comprising a
metallocene compound (Formula 1, below) together with an activator
such as a non-coordinating anion (NCA) (Formula 2, below) and
optionally a co-activator such as a trialkylaluminum, or with
methylaluminoxane (MAO) (Formula 3, below). ##STR1##
[0035] The term "catalyst system" is defined herein to mean a
catalyst precursor/activator pair, such as a metallocene/activator
pair. When "catalyst system" is used to describe such a pair before
activation, it means the unactivated catalyst (precatalyst)
together with an activator and, optionally, a co-activator (such as
a trialkyl aluminum compound). When it is used to describe such a
pair after activation, it means the activated catalyst and the
activator or other charge-balancing moiety. Furthermore, this
activated "catalyst system" may optionally comprise the
co-activator and/or other charge-balancing moiety. Optionally and
often, the co-activator, such as trialkylaluminum compound, is also
used as impurity scavenger.
[0036] The metallocene is selected from one or more compounds
according to Formula 1, above. In Formula 1, M is selected from
Group 4 transition metals, preferably zirconium (Zr), hafnium (Hf)
and titanium (Ti), L1 and L2 are independently selected from
cyclopentadienyl ("Cp"), indenyl, and fluorenyl, which may be
substituted or unsubstituted, and which may be partially
hydrogenated, A can be no atom, as in many un-bridged metallocenes
or A is an optional bridging group which if present, in preferred
embodiments is selected from dialkylsilyl, dialkylmethyl,
diphenylsilyl or diphenylmethyl, ethylenyl (--CH2--CH2--),
alkylethylenyl (--CR2--CR2--), where alkyl can be independently C1
to C16 alkyl radical or phenyl, tolyl, xylyl radical and the like,
and wherein each of the two X groups, Xa and Xb, are independently
selected from halides, OR(R is an alkyl group, preferably selected
from C1 to C5 straight or branched chain alkyl groups), hydrogen,
C1 to C16 alkyl or aryl groups, haloalkyl, and the like. Usually
relatively more highly substituted metallocenes give higher
catalyst productivity and wider product viscosity ranges and are
thus often more preferred.
[0037] In another embodiment, any of the polyalpha-olefins produced
herein preferably have a Bromine number of 1.8 or less as measured
by ASTM D 1159, preferably 1.7 or less, preferably 1.6 or less,
preferably 1.5 or less, preferably 1.4 or less, preferably 1.3 or
less, preferably 1.2 or less, preferably 1.1 or less, preferably
1.0 or less, preferably 0.5 or less, preferably 0.1 or less.
[0038] In another embodiment, any of the polyalpha-olefins produced
herein are hydrogenated and have a Bromine number of 1.8 or less as
measured by ASTM D 1159, preferably 1.7 or less, preferably 1.6 or
less, preferably 1.5 or less, preferably 1.4 or less, preferably
1.3 or less, preferably 1.2 or less, preferably 1.1 or less,
preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or
less.
[0039] In another embodiment, any of the polyalpha-olefins
described herein may have monomer units represented by the formula,
in addition to the all regular 1,2-connection. ##STR2##
[0040] where j, k and m are each, independently, 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n
is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to
50) as measured by proton NMR
[0041] In another embodiment, any of the polyalpha-olefins
described herein preferably have an Mw (weight average molecular
weight) of 100,000 or less, preferably between 100 and 80,000,
preferably between 250 and 60,000, preferably between 280 and
50,000, preferably between 336 and 40,000 g/mol.
[0042] In another embodiment, any of the polyalpha-olefins
described herein preferably have an Mn (number average molecular
weight) of 50,000 or less, preferably between 200 and 40,000,
preferably between 250 and 30,000, preferably between 500 and
20,000 g/mole.
[0043] In another embodiment, any of the polyalpha-olefins
described herein preferably have a molecular weight distribution
(MWD=Mw/Mn) of greater than 1 and less than 5, preferably less than
4, preferably less than 3, preferably less than 2.5. The MWD of
mPAO is always a function of fluid viscosity. Alternately any of
the polyalpha-olefins described herein preferably have an Mw/Mn of
between 1 and 2.5, alternately between 1 and 3.5, depending on
fluid viscosity.
[0044] The Mw, Mn and Mz are measured by GPC method using a column
for medium to low molecular weight polymers, tetrahydrofuran as
solvent and polystyrene as calibration standard, correlated with
the fluid viscosity according to a power equation.
[0045] In a preferred embodiment of this invention, any PAO
described herein may have a pour point of less than 0.degree. C.
(as measured by ASTM D 97), preferably less than -10.degree. C.,
preferably less than -20.degree. C., preferably less than
-25.degree. C., preferably less than -30.degree. C., preferably
less than -35.degree. C., preferably less than -50.degree.,
preferably between -10 and -80.degree. C., preferably between
-15.degree. C. and -70.degree. C.
[0046] In a preferred embodiment of this invention, any PAO
described herein may have a kinematic viscosity (at 40.degree. C.
as measured by ASTM D 445) from about 4 to about 50,000 cSt,
preferably from about 5 cSt to about 30,000 cSt at 40.degree. C.,
alternately from about 4 to about 100,000 cSt, preferably from
about 6 cSt to about 50,000 cSt, preferably from about 10 cSt to
about 30,000 cSt at 40.degree. C.
[0047] In another embodiment, any polyalpha-olefin described herein
may have a kinematic viscosity at 100.degree. C. from about 1.5 to
about 5,000 cSt, preferably from about 2 to about 3,000 cSt,
preferably from about 3 cSt to about 1,000 cSt, more preferably
from about 4 cSt to about 1,000 cSt, and yet more preferably from
about 8 cSt to about 500 cSt as measured by ASTM D445. The PAOs
preferably have viscosities in the range of 2 to 500 cSt at
100.degree. C. in one embodiment, and from 2 to 3000 cSt at
100.degree. C. in another embodiment, and from 3.2 to 300 cSt in
another embodiment. Alternately, the polyalpha-olefin has a KV100
of less than 200 cSt.
[0048] In another embodiment, any polyalpha olefin described herein
may have a kinematic viscosity at 100.degree. C. from 3 to 10 cSt
and a flash point of 150.degree. C. or more, preferably 200.degree.
C. or more (as measured by ASTM D 56).
[0049] In another embodiment, any polyalpha olefin described herein
may have a dielectric constant of 2.5 or less (1 kHz at 23.degree.
C. as determined by ASTM D 924).
[0050] In another embodiment, any polyalpha olefin described herein
may have a specific gravity of 0.75 to 0.96 g/cm.sup.3, preferably
0.80 to 0.94 g/cm.sup.3.
[0051] In another embodiment, any polyalpha olefin described herein
may have a viscosity index (VI) of 100 or more, preferably 120 or
more, preferably 130 or more, alternately, form 120 to 450,
alternately from 100 to 400, alternately from 120 to 380,
alternately from 100 to 300, alternately from 140 to 380,
alternately from 180 to 306, alternately from 252 to 306,
alternately the viscosity index is at least about 165, alternately
at least about 187, alternately at least about 200, alternately at
least about 252. For many lower viscosity fluids made from 1-decene
or 1-decene equivalent feeds (KV100.degree. C. of 3 to 10 cSt), the
preferred VI range is from 100 to 180. Viscosity index is
determined according to ASTM Method D 2270-93 [1998].
[0052] All kinematic viscosity values reported for fluids herein
are measured at 100.degree. C. unless otherwise noted. Dynamic
viscosity can then be obtained by multiplying the measured
kinematic viscosity by the density of the liquid. The units for
kinematic viscosity are in m.sup.2/s, commonly converted to cSt or
centistokes (1 cSt=10-6 m.sup.2/s or 1 cSt=1 mm.sup.2/sec).
[0053] One embodiment is a new class of poly-alpha-olefins, which
have a unique chemical composition characterized by a high degree
of linear branches and very regular structures with some unique
head-to-head connections at the end position of the polymer chain.
The polyalpha-olefins, whether homo-polymers or co-polymers, can be
isotactic, syndiotactic or atactic polymers, or have combination of
the tacticity. The new poly-alpha-olefins when used by themselves
or blended with other fluids have unique lubrication
properties.
[0054] Another embodiment is a new class of hydrogenated
poly-alpha-olefins having a unique composition which is
characterized by a high percentage of unique head-to-head
connection at the end position of the polymer and by a reduced
degree tacticity compared to the product before hydrogenation. The
new poly-alpha-olefins when used by itself or blended with another
fluid have unique lubrication properties.
[0055] This improved process to produce these polymers employs
metallocene catalysts together with one or more activators (such as
an alumoxane or a non-coordinating anion) and optionally with
co-activators such as trialkylaluminum compounds. The metallocene
catalyst can be a bridged or unbridged, substituted or
unsubstituted cyclopentadienyl, indenyl or fluorenyl compound. One
preferred class of catalysts are highly substituted metallocenes
that give high catalyst productivity and higher product viscosity.
Another preferred class of metallocenes are bridged and substituted
cyclopentadienes. Another preferred class of metallocenes are
bridged and substituted indenes or fluorenes. One aspect of the
processes described herein also includes treatment of the feed
olefins to remove catalyst poisons, such as peroxides, oxygen,
sulfur, nitrogen-containing organic compounds, and or acetylenic
compounds. This treatment is believed to increase catalyst
productivity, typically more than 5 fold, preferably more than 10
fold.
[0056] A preferred embodiment is a process to produce a
polyalpha-olefin comprising:
[0057] 1) contacting at least one alpha-olefin monomer having 3 to
30 carbon atoms with a metallocene compound and an activator under
polymerization conditions wherein hydrogen, if present, is present
at a partial pressure of 200 psi (1379 kPa) or less, based upon the
total pressure of the reactor (preferably 150 psi (1034 kPa) or
less, preferably 100 psi (690 kPa) or less, preferably 50 psi (345
kPa) or less, preferably 25 psi (173 kPa) or less, preferably 10
psi (69 kPa) or less (alternately the hydrogen, if present in the
reactor at 30,000 ppm or less by weight, preferably 1,000 ppm or
less preferably 750 ppm or less, preferably 500 ppm or less,
preferably 250 ppm or less, preferably 100 ppm or less, preferably
50 ppm or less, preferably 25 ppm or less, preferably 10 ppm or
less, preferably 5 ppm or less), and wherein the alpha-olefin
monomer having 3 to 30 carbon atoms is present at 10 volume % or
more based upon the total volume of the
catalyst/activator/co-activator solutions, monomers, and any
diluents or solvents present in the reaction; and
[0058] 2) obtaining a polyalpha-olefin, optionally hydrogenating
the PAO, and obtaining a PAO, comprising at least 50 mole % of a C3
to C30 alpha-olefin monomer, wherein the polyalpha-olefin has a
kinematic viscosity at 100.degree. C. of 5000 cSt or less, and the
polyalpha-olefin comprises Z mole % or more of units represented by
the formula: ##STR3## where j, k and m are each, independently, 1,
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,
21, or 22, n is an integer from 1 to 350, and
[0059] An alternate embodiment is a process to produce a
polyalpha-olefin comprising:
[0060] 1) contacting a feed stream comprising one or at least one
alpha-olefin monomer having 3 to 30 carbon atoms with a metallocene
catalyst compound and a non-coordinating anion activator or
alkylalumoxane activator, and optionally an alkyl-aluminum
compound, under polymerization conditions wherein the alpha-olefin
monomer having 3 to 30 carbon atoms is present at 10 volume % or
more based upon the total volume of the
catalyst/activator/co-activator solution, monomers, and any
diluents or solvents present in the reactor and where the feed
alpha-olefin, diluent or solvent stream comprises less than 300 ppm
of heteroatom containing compounds; and obtaining a
polyalpha-olefin comprising at least 50 mole % of a C5 to C24
alpha-olefin monomer where the polyalpha-olefin has a kinematic
viscosity at 100.degree. C. of 5000 cSt or less. Preferably,
hydrogen, if present is present in the reactor at 30,000 ppm or
less by weight, preferably 1,000 ppm or less preferably 750 ppm or
less, preferably 500 ppm or less, preferably 250 ppm or less,
preferably 100 ppm or less, preferably 50 ppm or less, preferably
25 ppm or less, preferably 10 ppm or less, preferably 5 ppm or
less.
[0061] An alternate embodiment is a process to produce a
polyalpha-olefin comprising:
[0062] 1) contacting a feed stream comprising at least one
alpha-olefin monomer having 3 to 30 carbon atoms with a metallocene
catalyst compound and a non-coordinating anion activator or
alkylalumoxane activator, and optionally an alkyl-aluminum
compound, under polymerization conditions wherein the alpha-olefin
monomer having 3 to 30 carbon atoms is present at 10 volume % or
more based upon the total volume of the
catalyst/activator/co-activator solution, monomers, and any
diluents or solvents present in the reactor and where the feed
alpha-olefin, diluent or solvent stream comprises less than 300 ppm
of heteroatom containing compounds which; and obtaining a
polyalpha-olefin comprising at least 50 mole % of a C5 to
C24alpha-olefin monomer where the polyalpha-olefin has a kinematic
viscosity at 100.degree. C. of 5000 cSt or less; Alternately, in
this process described herein hydrogen, if present, is present in
the reactor at 1000 ppm or less by weight, preferably 750 ppm or
less, preferably 500 ppm or less, preferably 250 ppm or less,
preferably 100 ppm or less, preferably 50 ppm or less, preferably
25 ppm or less, preferably 10 ppm or less, preferably 5 ppm or
less.
[0063] 2) isolating the lube fraction polymers and then contacting
this lube fraction with hydrogen under typical hydrogenation
conditions with hydrogenation catalyst to give fluid with bromine
number below 1.8, or alternatively, isolating the lube fraction
polymers and then contacting this lube fraction with hydrogen under
more severe conditions with hydrogenation catalyst to give fluid
with bromine number below 1.8 and with reduce mole % of mm
components than the unhydrogenated polymers. The hydrogen pressure
for this process is usually in the range from 50 psi to 3000 psi,
preferably 200 to 2000 psi, preferably 500 to 1500 psi.
Molecular Weight Distribution (MWD)
[0064] Molecular weight distribution is a function of viscosity.
The higher the viscosity the higher the molecular weight
distribution. FIG. 1 is a graph showing the molecular weight
distribution as a function of viscosity at Kv100.degree. C. The
circles represent the prior art prior art PAO. The squares and
upper triangles represent the new metallocene catalyzed PAOs. Line
1 represents the preferred lower range of molecular weight
distribution for the high viscosity metallocene catalyzed PAO. Line
3 represents preferred upper range of the molecular weight
distribution for the high viscosity metallocene catalyzed PAO.
Therefore, the region bounded by lines 1 and 3 represents the
preferred molecular weight distribution region of the new
metallocene catalyzed PAO. Line 2 represents the desirable and
typical MWD of actual experimental samples of the metallocene PAO
made from 1-decene. Line 5 represents molecular weight distribution
of the prior art PAO.
[0065] Equation 1 represents the algorithm for line 5 or the
average molecular weight distribution of the prior art PAO. Whereas
equations 2, 3, and 4 represent lines 1, 3 and 2 respectively.
MWD=0.2223+1.0232*log(Kv at 100.degree. C. in cSt) Eq. 1
MWD=0.41667+0.725*log(Kv at 100.degree. C. in cSt) Eq. 2
MWD=0.8+0.3*log(Kv at 100.degree. C. in cSt) Eq. 3
MWD=0.66017+0.44922*log(Kv at 100.degree. C. in cSt) Eq. 4
[0066] In at least one embodiment, the molecular weight
distribution is at least 10 percent less than equation 1. In a
preferred embodiment the molecular weight distribution is less than
equation 2 and in a most preferred embodiment the molecular weight
distribution is less than equation 2 and more than equation 4.
[0067] Table 1 is a table demonstrating the differences between
metallocene catalyzed PAO ("mPAO") and current high viscosity prior
art PAO (cHVI-PAO). Examples 1 to 8 in the Table 1 were prepared
from different feed olefins using metallocene catalysts. The
metallocene catalyst system, products, process and feeds were
described in patent applications Nos. PCT/US2006/021399 and
PCT/US2006/021231. The mPAOs samples in Table were made from C10,
C6,12, C6 to C18, C6,10,14-LAOs. Examples 1 to 7 samples all have
very narrow molecular weight distribution (MWD). The MWD of mPAO
depends on fluid viscosity as shown in FIG. 1. TABLE-US-00001 TABLE
1 Example No. 1 2 3 4 5 6 7 8 9 10 11 sample mPAO mPAO mPAO mPAO
mPAO mPAO mPAO mPAO cHVI- cHVI- cHVI- type PAO PAO PAO Feed LAO C6/
C6- C6- C10 C6, 10, 14 C6,10,14 C10 C10 C10 C10 C10 C12 C18 C18
(25/60/15%) (25/60/15%) 100.degree. C. 150 151 540 671 460 794.35
1386.63 678.1 150 300 1,000 Kv, cS 40.degree. C. 1701 1600 6642
6900 5640 10318 16362 6743 1500 3100 10,000 Kv, cS VI 199 207 257
248 275 321 303 218 241 307 Pour, -33 -36 -21 -18 nd nd -12 -33 -27
-18 .degree. C. MWD by GPC Mw 7,409 8,089 17,227 19772 16149 20273
31769 29333 8,974 12,511 32,200 MWD 1.79 2.01 1.90 1.98 2.35 2.18
1.914 5.50 2.39 2.54 4.79 % Visc Change by TRB Test (a) 20 hrs
-0.33 -0.65 -2.66 -3.64 -4.03 -8.05 -19.32 -29.11 -7.42 -18.70
-46.78 100 hrs -0.83 -0.70 -1.07 1.79 nd nd nd nd nd -21.83 -51.09
(a) CEC L-45-A-99 Taper Rolling Bearing/C. (20 hours) (KRL test 20
hours) at SouthWest Research Institute
[0068] When Example 1 to 7 samples were subjected to tapered roller
bearing ("TRB") test, they show very low viscosity loss after 20
hours shearing or after extended 100 hours shearing (TRB).
Generally, shear stability is a function of fluid viscosity. Lower
viscosity fluids have minimal viscosity losses of less than 10%.
When fluid viscosity is above 1000 cS as in Example 7, the fluid
loss is approximately 19% viscosity. Example 8 is a metallocene PAO
with MWD of 5.5. This metallocene PAO shows significant amount of
viscosity loss at 29%.
[0069] Examples 9, 10 and 11 are comparative examples. The high
viscosity PAO are made according to methods described in U.S. Pat.
Nos. 4,827,064 and 4,827,073. They have broad MWD and therefore
poor shear stability in TRB test.
[0070] The comparison of shear stability as a function of fluid
viscosity for mPAO with narrow MWD vs. cHVI-PAO is summarized in
FIG. 2. This graph demonstrates that the mPAO profile shown as line
21 has much improved shear stability over wide viscosity range when
compared to the cHVI-PAO profile shown as line 23.
[0071] These examples demonstrated the importance of MWD effect on
shear stability. Accordingly, The higher viscosity base stocks with
tighter molecular weight distributions provide favorable shear
stability even at high viscosities.
Lubricant Formulation
[0072] The formulation is based on extreme modal blends of high
viscosity synthetic group IV PAO. In a preferred embodiment, a High
Viscosity Index, metallocene-catalyzed PAO of greater than 300 cSt
is blended with a low-viscosity base stock PAO and/or with one or
more of Gr V base stocks, such as an ester, a polyalkylene glycol
or an alkylated aromatic, as a co-base for additive solubility. A
detailed description of suitable Gr V base stocks can be found in
"Synthetics, Mineral Oils and Bio-Based Lubricants, Chemistry and
Technology" Edited by L. R. Rudnick, published by CRC Press, Taylor
& Francis, 2005. The esters of choice are dibasic esters (such
as adipate ester, ditridecyl adipate), mono-basic esters, polyol
esters and phthalate esters. The alkylated aromatics of choice are
alkylbenzene, alkylated naphthalene and other alkylated aromatics
such as alkylated diphenylether, diphenylsulfide, biphenyl, etc. We
have found that this unique base stock combination can impart
enhanced worm gear efficiency, improved air-release property and
decrease in operating temperature.
[0073] Also, unexpected and significant air release benefits result
from this discovery. Specifically, decreased air release times
according to ASTM D 3427. These air release benefits are manifest
in a decrease of as much as 75% of the standard release times of
gear oil viscosity-grade lubricants. In addition to the above
mentioned benefits, we also discovered, significant improvements in
low temperature performance (reduction in pour point).
[0074] In one embodiment, the lubricant oil comprises at least two
base stock blends of oil. The first base stock blend comprises
lubricant oil with a viscosity of over 300 cSt, and more preferably
over 400 cSt, Kv100.degree. C. Most preferably, the base stock is
over 570 cSt, Kv100.degree. C. but less than 5000 cSt. The first
base stock has a molecular weight distribution less than 10 percent
of equation 1. In an even more preferred embodiment the first base
stock is a metallocene catalyzed PAO with a viscosity of at least
300, more preferably 400 and most preferably at least 600 cSt.
[0075] The second base stock blend comprises a lubricant oil with a
viscosity of less than 60 cSt and preferably less than 40 cSt, and
most preferably less than 10 cSt. Preferably, the viscosity of the
second lubricant should be at least 1.5 cSt. Even more preferable
is a viscosity of between 1.7 and 40 cSt.
[0076] The air release performance enhancement of the current
invention is an unexpected result since the typical performance of
these very viscous oils (ISO 460) is typically an air release time
to 0.2% air in the ASTM D3427 test to be 20 minutes or more. Also,
the low temperature performance of these novel formulations shows
significant improvement as demonstrated in the ASTM D97 and D5133
data shown in Table 2. The air release performance enhancement of
the current invention is unexpected and novel since the typical
performance of these very viscous oils (ISO 460) is typically an
air release time to 0.2% air in the ASTM D3427 test to be 20
minutes or more. TABLE-US-00002 TABLE 2 ASTM D3427 (75C) Results
Commercially Current Invention availableISO 460 Air Release in
Minutes ISO 460 Gear Oil Gear Oil Time to 0.1% air 6.9 25 Time to
0.2% air 5.2 21
[0077] 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/or 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. Table 3 summarizes
properties of each of these five groups. All discussion of Gr I to
V base stocks can be found in "Synthetics, Mineral Oils and
Bio-Based Lubricants, Chemistry and Technology" Edited by L. R.
Rudnick, published by CRC Press, Taylor & Francis, 2005.
[0078] Group VI in Table 3 are Polyinternal olefins ("PIO").
Polyinternal olefins are long-chain hydrocarbons, typically a
linear backbone with some branching randomly attached; they are
obtained by oligomerization of internal n-olefins. The catalyst is
usually a BF3 complex with a proton source that leads to a cationic
polymerization, or promoted BF3 or AlCl3 catalyst system. The
process to produce polyinternal olefins (PIO) consists of four
steps: reaction, neutralization/washing, hydrogenation and
distillation. These steps are somewhat similar to PAO process. PIO
are typically available in low viscosity grades, 4 cS, 6 cS and 8
cS. If necessary, low viscosity, 1.5 to 3.9 cS can also be made
conveniently by the BF3 process or other cationic processes.
Typically, the n-olefins used as starting material are n-C12-C18
internal olefins, more preferably, n-C14-C116 olefins are used. PIO
can be made with VI and pour points very similar to PAO, only
slightly inferior. They can be used in engine and industrial
lubricant formulations. For more detailed discussion, see Chapter
2, Polyinternalolefins in the book, "Synthetics, Mineral Oils, and
Bio-Based Lubricants--Chemistry and Technology" Edited by Leslie R.
Rudnick, p. 37-46, published by CRC Press, Taylor & Francis
Group, 2006; or "Polyinternal Olefins" by Corsico, G.; Mattei, L.;
Roselli, A.; Gommellini, Carlo. EURON, Milan, Italy. Chemical
Industries (Dekker) (1999), 77(Synthetic Lubricants and
High-Performance Functional Fluids, (2nd Edition)), 53-62.
Publisher: Marcel Dekker, Inc. PIO was classified by itself as
Group VI fluid in API base stock classification. TABLE-US-00003
TABLE 3 Base Stock Properties Saturates Sulfur Viscosity Index
Group I <90% and/or >0.03% and .gtoreq.80 and <120 Group
II .gtoreq.90% and .ltoreq.0.03% and .gtoreq.80 and <120 Group
III .gtoreq.90% and .ltoreq.0.03% and .gtoreq.120 Group IV
Polyalphaolefins (PAO) Group V All other base oil stocks not
included in Groups I, II, III, or IV Group VI Polyinternal olefins
(PIO)
[0079] In a preferred embodiment, the base stocks include at least
one base stock of synthetic oils and most preferably include at
least one base stock of API group IV Poly Alpha Olefins. Synthetic
oil for purposes of this application shall include all oils that
are not naturally occurring mineral oils. Naturally occurring
mineral oils are often referred to as API Group I oils.
[0080] A new type of PAO lubricant was introduced by U.S. Pat. Nos.
4,827,064 and 4,827,073 (Wu). These PAO materials, which are
produced by the use of a reduced valence state chromium catalyst,
are olefin oligomers or polymers which are characterized by very
high viscosity indices which give them very desirable properties to
be useful as lubricant base stocks and, with higher viscosity
grades; as VI improvers. They are referred to as High Viscosity
Index PAOs or HVI-PAOs. The relatively low molecular weight high
viscosity PAO materials were found to be useful as lubricant base
stocks whereas the higher viscosity PAOs, typically with
viscosities of 100 cSt or more, e.g. in the range of 100 to 1,000
cSt, were found to be very effective as viscosity index improvers
for conventional PAOs and other synthetic and mineral oil derived
base stocks.
[0081] Various modifications and variations of these high viscosity
PAO materials are also described in the following U.S. patents to
which reference is made: U.S. Pat. Nos. 4,990,709; 5,254,274;
5,132,478; 4,912,272; 5,264,642; 5,243,114; 5,208,403; 5,057,235;
5,104,579; 4,943,383; 4,906,799. These oligomers can be briefly
summarized as being produced by the oligomerization of 1-olefins in
the presence of a metal oligomerization catalyst which is a
supported metal in a reduced valence state. The preferred catalyst
comprises a reduced valence state chromium on a silica support,
prepared by the reduction of chromium using carbon monoxide as the
reducing agent. The oligomerization is carried out at a temperature
selected according to the viscosity desired for the resulting
oligomer, as described in U.S. Pat. Nos. 4,827,064 and 4,827,073.
Higher viscosity materials may be produced as described in U.S.
Pat. No. 5,012,020 and U.S. Pat. No. 5,146,021 where
oligomerization temperatures below about 90.degree. C. are used to
produce the higher molecular weight oligomers. In all cases, the
oligomers, after hydrogenation when necessary to reduce residual
unsaturation, have a branching index (as defined in U.S. Pat. Nos.
4,827,064 and 4,827,073) of less than 0.19. Overall, the HVI-PAO
normally have a viscosity in the range of about 12 to 5,000
cSt.
[0082] Furthermore, the HVI-PAOs generally can be characterized by
one or more of the following: C30-C1300 hydrocarbons having a
branch ratio of less than 0.19, a weight average molecular weight
of between 300 and 45,000, a number average molecular weight of
between 300 and 18,000, a molecular weight distribution of between
1 and 5. Particularly preferred HVI-PAOs are fluids with
100.degree. C. viscosity ranging from 5 to 5000 cSt. In another
embodiment, viscosities of the HVI-PAO oligomers measured at
100.degree. C. range from 3 centistokes ("cSt") to 15,000 cSt.
Furthermore, the fluids with viscosity at 100.degree. C. of 3 cSt
to 5000 cSt have VI calculated by ASTM method D2270 greater than
130. Usually they range from 130 to 350. The fluids all have low
pour points, below -15.degree. C.
[0083] The HVI-PAOs can further be characterized as hydrocarbon
compositions comprising the polymers or oligomers made from
1-alkenes, either by itself or in a mixture form, taken from the
group consisting of C6-C20 1-alkenes. Examples of the feeds can be
1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc. or
mixture of C6 to C14 1-alkenes or mixture of C6 to C20 1-alkenes,
C6 and C12 1-alkenes, C6 and C14 1-alkenes, C6 and C16 1-alkenes,
C6 and C18 1-alkenes, C8 and C10 1-alkenes, C8 and C12 1-alkenes,
C8, C10 and C12 1-alkenes, and other appropriate combinations.
[0084] The lube products usually are distilled to remove any low
molecular weight compositions such as these boiling below
600.degree. F., or with carbon number less than C20, if they are
produced from the polymerization reaction or are carried over from
the starting material. This distillation step usually improves the
volatility of the finished fluids. In certain special applications,
or when no low boiling fraction is present in the reaction mixture,
this distillation is not necessary. Thus the whole reaction product
after removing any solvent or starting material can be used as lube
base stock or for the further treatments.
[0085] The lube fluids made directly from the polymerization or
oligomerization process usually have unsaturated double bonds or
have olefinic molecular structure. The amount of double bonds or
unsaturation or olefinic components can be measured by several
methods, such as bromine number (ASTM 1159), bromine index (ASTM
D2710) or other suitable analytical methods, such as NMR, IR, etc.
The amount of the double bond or the amount of olefinic
compositions depends on several factors--the degree of
polymerization, the amount of hydrogen present during the
polymerization process and the amount of other promoters which
participate in the termination steps of the polymerization process,
or other agents present in the process. Usually, the amount of
double bonds or the amount of olefinic components is decreased by
the higher degree of polymerization, the higher amount of hydrogen
gas present in the polymerization process, or the higher amount of
promoters participating in the termination steps.
[0086] It was known that, usually, the oxidative stability and
light or UV stability of fluids improves when the amount of
unsaturation double bonds or olefinic contents is reduced.
Therefore it is necessary to further hydrotreat the polymer if they
have high degree of unsaturation. Usually, the fluids with bromine
number of less than 5, as measured by ASTM D1159, is suitable for
high quality base stock application. Of course, the lower the
bromine number, the better the lube quality. Fluids with bromine
number of less than 3 or 2 are common. The most preferred range is
less than 1 or less than 0.1. The method to hydrotreat to reduce
the degree of unsaturation is well known in literature [U.S. Pat.
No. 4,827,073, example 16). In some HVI-PAO products, the fluids
made directly from the polymerization already have very low degree
of unsaturation, such as those with viscosities greater than 150
cSt at 100.degree. C. They have bromine numbers less than 5 or even
below 2. In these cases, we can chose to use as is without
hydrotreating, or we can choose to hydrotreating to further improve
the base stock properties.
[0087] Another type of PAO, classified as Group IV base stock and
used extensively in many synthetic or partial synthetic industrial
lubricants, is produced by oligomerization or polymerization of
linear alpha-olefins of C6 to C16 by promoted BF3 or AlCl3
catalysts. This type of PAO is available in many viscosity grades
ranging from 1.7 cS to 100 cS from ExxonMobil Chemical Co.
[0088] Base stocks having a high paraffinic/naphthenic and
saturation nature of greater than 90 weight percent can often be
used advantageously in certain embodiments. Such base stocks
include Group II and/or Group III hydroprocessed or hydrocracked
base stocks, or their synthetic counterparts such as
polyalphaolefin oils, GTL or similar base oils or mixtures of
similar base oils. For purposes of this application synthetic bases
stocks shall include Group II, Group III, group IV and Group V base
stocks.
[0089] A more specific example embodiment, is the combination of
high viscosity metallocene catalyzed PAO having a molecular weight
distribution (MWD) as a function of viscosity at least 10 percent
less than the algorithm: [MWD=0.2223+1.0232*log(Kv at 100.degree.
C. in cSt)] with a low viscosity Poly Alpha Olefin ("PAO")
including PAOs with a viscosity of less than 6 cSt, and more
preferably with a viscosity between 1.5 cSt or 4 cSt, Kv100.degree.
C. and even more preferably with a small amount of Group V base
stocks, including esters, polyalkylene glycols, or alkylated
aromatics. The Gr V base stocks can be used as an additional base
stock or as a co-base stock with either the first and second base
stocks for additive solubility. The preferred ester is an alkyl
adipate, a polyol ester or aromatic ester, such as phthalate ester.
The preferred alkyl aromatics are alkylbenzenes or
alkylnaphthalenes. The preferred polyalkylene glycols are liquid
polymers or copolymers made from ethylene oxide, propylene oxide,
butylenes oxides or higher alkylene oxides with some degree of
compatibility with PAO, other hydrocarbon fluids, GTL or mineral
oils.
[0090] Gas to liquid (GTL) base stocks can also be preferentially
used with the components of this invention as a portion or all of
the base stocks used to formulate the finished lubricant. We have
discovered, favorable improvement when the components of this
invention are added to lubricating systems comprising primarily
Group II, Group III and/or GTL base stocks compared to lesser
quantities of alternate fluids.
[0091] 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
feedstocks such as hydrogen, carbon dioxide, carbon monoxide,
water, methane, ethane, ethylene, acetylene, propane, propylene,
propyne, butane, butylenes, and butynes. GTL base stocks and 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 feedstocks. GTL base stock(s) include oils boiling in
the lube oil boiling range separated/fractionated from GTL
materials such as by, for example, distillation or thermal
diffusion, and subsequently subjected to well-known catalytic or
solvent dewaxing processes to produce lube oils of reduced/low pour
point; wax isomerates, comprising, for example, hydroisomerized or
isodewaxed synthesized hydrocarbons; hydro-isomerized or isodewaxed
Fischer-Tropsch ("F-T") material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); preferably
hydroisomerized or isodewaxed F-T hydrocarbons or hydroisomerized
or isodewaxed F-T waxes, hydroisomerized or isodewaxed synthesized
waxes, or mixtures thereof.
[0092] GTL base stock(s) derived from GTL materials, especially,
hydroisomerized/isodewaxed F-T material derived base stock(s), and
other hydroisomerized/isodewaxed wax derived base stock(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,
preferably from about 3 mm.sup.2/s to about 50 mm.sup.2/s, more
preferably from about 3.5 mm.sup.2/s to about 30 mm.sup.2/s, as
exemplified by a GTL base stock derived by the isodewaxing of F-T
wax, which has a kinematic viscosity of about 4 mm.sup.2/s at
100.degree. C. and a viscosity index of about 130 or greater. The
term GTL base oil/base stock and/or wax isomerate base oil/base
stock as used herein and in the claims is to be understood as
embracing individual fractions of GTL base stock/base oil or wax
isomerate base stock/base oil as recovered in the production
process, mixtures of two or more GTL base stocks/base oil fractions
and/or wax isomerate base stocks/base oil fractions, as well as
mixtures of one or two or more low viscosity GTL base stock(s)/base
oil fraction(s) and/or wax isomerate base stock(s)/base oil
fraction(s) with one, two or more high viscosity GTL base
stock(s)/base oil fraction(s) and/or wax isomerate base
stock(s)/base oil fraction(s) to produce a bi-modal blend wherein
the blend exhibits a viscosity within the aforesaid recited range.
Reference herein to Kinematic Viscosity refers to a measurement
made by ASTM method D445.
[0093] GTL base stocks and base oils derived from GTL materials,
especially hydroisomerized/isodewaxed F-T material derived base
stock(s), and other hydroisomerized/isodewaxed wax-derived base
stock(s), such as wax hydroisomerates/isodewaxates, which can be
used as base stock components of this invention are further
characterized typically as having pour points of about -5.degree.
C. or lower, preferably about -10.degree. C. or lower, more
preferably about -15.degree. C. or lower, still more preferably
about -20.degree. C. or lower, and under some conditions may have
advantageous pour points of about -25.degree. C. or lower, with
useful pour points of about -30.degree. C. to about -40.degree. C.
or lower. If necessary, a separate dewaxing step may be practiced
to achieve the desired pour point. References herein to pour point
refer to measurement made by ASTM D97 and similar automated
versions.
[0094] The GTL base stock(s) derived from GTL materials, especially
hydroisomerized/isodewaxed F-T material derived base stock(s), and
other hydroisomerized/isodewaxed wax-derived base stock(s) which
are base stock components which can be used in this invention are
also characterized typically as having viscosity indices of 80 or
greater, preferably 100 or greater, and more preferably 120 or
greater. Additionally, in certain particular instances, viscosity
index of these base stocks may be preferably 130 or greater, more
preferably 135 or greater, and even more preferably 140 or greater.
For example, GTL base stock(s) that derive from GTL materials
preferably F-T materials especially F-T wax generally have a
viscosity index of 130 or greater. References herein to viscosity
index refer to ASTM method D2270.
[0095] In addition, the GTL base stock(s) are typically highly
paraffinic of greater than 90 percent 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
stocks and base oils typically have very low sulfur and nitrogen
content, generally containing less than about 10 ppm, and more
typically less than about ppm of each of these elements. The sulfur
and nitrogen content of GTL base stock and base oil obtained by the
hydroisomerization/isodewaxing of F-T material, especially F-T wax
is essentially nil.
[0096] In a preferred embodiment, the GTL base stock(s) comprises
paraffinic materials that consist predominantly of non-cyclic
isoparaffins and only minor amounts of cycloparaffins. These GTL
base stock(s) typically comprise paraffinic materials that consist
of greater than 60 wt % non-cyclic isoparaffins, preferably greater
than 80 wt % non-cyclic isoparaffins, more preferably greater than
85 wt % non-cyclic isoparaffins, and most preferably greater than
90 wt % non-cyclic isoparaffins.
[0097] Useful compositions of GTL base stock(s), hydroisomerized or
isodewaxed F-T material derived base stock(s), and wax-derived
hydroisomerized/isodewaxed base stock(s), such as wax
isomerates/isodewaxates, are recited in U.S. Pat. Nos. 6,080,301;
6,090,989, and 6,165,949 for example.
[0098] We have discovered that this unique base stock combination
can impart even further favorable properties when combined with
specific additive systems. The additives include various
commercially available gear oil packages. These additive packages
include a high performance series of components that include
antiwear, antioxidant, defoamant, demulsifier, detergent,
dispersant, metal passivation, and rust inhibition additive
chemistries to deliver desired performance.
[0099] The additives may be chosen to modify various properties of
the lubricating oils. For gear oils, the additives should provide
the following properties, antiwear protection, rust protection,
micropitting protection, friction reduction, and improved
filterability. Persons skilled in the art will recognize various
additives that can be chosen to achieve favorable properties
including favorable properties for gear oil applications.
[0100] The final lubricant should comprise a first lubricant base
stock having a viscosity of greater than 300 cSt, Kv100.degree. C.
The first lubricant base stock should comprise of at least 10
percent and no more than 70 percent of the final lubricant.
Preferred range is at least 20 percent to 60 percent. The second
base stock having a viscosity less than 100 cSt should comprise at
least 20 percent and no more than 70 percent of the final base
stock total. The amount of Group V base stocks, such as esters,
polyalkylene glycols or alkylated aromatics and/or additive can be
up to 90 percent of the final lubricant total with a proportional
decrease in the acceptable ranges of first and second base stocks.
The preferred range of group V, such as esters and additives is
between 10 and 90 percent. Sometimes, some Group I or II base stock
can be used in the formulation together with ester or alkylated
aromatics or as a total substitute.
[0101] In various embodiments, it will be understood that additives
well known as functional fluid additives in the art, can also be
incorporated in the functional fluid composition of the invention,
in relatively small amounts, if desired; frequently, less than
about 0.001% up to about 10-20% or more. In one embodiment, at
least one oil additive is added from the group consisting of
antioxidants, stabilizers, antiwear additives, dispersants,
detergents, antifoam additives, viscosity index improvers, copper
passivators, metal deactivators, rust inhibitors, corrosion
inhibitors, pour point depressants, demulsifiers, anti-wear agents,
extreme pressure additives and friction modifiers. The additives
listed below are non-limiting examples and are not intented to
limit the claims.
[0102] Dispersants should contain the alkenyl or alkyl group R has
an Mn value of about 500 to about 5000 and an Mw/Mn ratio of about
1 to about 5. The preferred Mn intervals depend on the chemical
nature of the agent improving filterability. Polyolefinic polymers
suitable for the reaction with maleic anhydride or other acid
materials or acid forming materials, include polymers containing a
predominant quantity of C.sub.2 to C.sub.5 monoolefins, for
example, ethylene, propylene, butylene, isobutylene and pentene. A
highly suitable polyolefinic polymer is polyisobutene. The succinic
anhydride preferred as a reaction substance is PIBSA, that is,
polyisobutenyl succinic anhydride.
[0103] If the dispersant contains a succinimide comprising the
reaction product of a succinic anhydride with a polyamine, the
alkenyl or alkyl substituent of the succinic anhydride serving as
the reaction substance consists preferably of polymerised isobutene
having an Mn value of about 1200 to about 2500. More
advantageously, the alkenyl or alkyl substituent of the succinic
anhydride serving as the reaction substance consists in a
polymerised isobutene having an Mn value of about 2100 to about
2400. If the agent improving filterability contains an ester of
succinic acid comprising the reaction product of a succinic
anhydride and an aliphatic polyhydric alcohol, the alkenyl or alkyl
substituent of the succinic anhydride serving as the reaction
substance consists advantageously of a polymerised isobutene having
an Mn value of 500 to 1500. In preference, a polymerised isobutene
having an Mn value of 850 to 1200 is used.
[0104] Amides suitable uses of amines include antiwear agents,
extreme pressure additives, friction modifiers or Dispersants. The
amides which are utilized in the compositions of the present
invention may be amides of mono- or polycarboxylic acids or
reactive derivatives thereof. The amides may be characterized by a
hydrocarbyl group containing from about 6 to about 90 carbon atoms;
each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl,
hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbyl group,
provided that both are not hydrogen; each is, independently, a
hydrocarbylene group containing up to about 10 carbon atoms; Alk is
an alkylene group containing up to about 10 carbon atoms.
[0105] The amide can be derived from a monocarboxylic acid, a
hydrocarbyl group containing from 6 to about 30 or 38 carbon atoms
and more often will be a hydrocarbyl group derived from a fatty
acid containing from 12 to about 24 carbon atoms.
[0106] The amide is derived from a di- or tricarboxylic acid, will
contain from 6 to about 90 or more carbon atoms depending on the
type of polycarboxylic acid. For example, when the amide is derived
from a dimer acid, will contain from about 18 to about 44 carbon
atoms or more, and amides derived from trimer acids generally will
contain an average of from about 44 to about 90 carbon atoms. Each
is independently hydrogen or a hydrocarbyl, aminohydrocarbyl,
hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbon group
containing up to about 10 carbon atoms. It may be independently
heterocyclic substituted hydrocarbyl groups wherein the
heterocyclic substituent is derived from pyrrole, pyrroline,
pyrrolidine, morpholine, piperazine, piperidine, pyridine,
pipecoline, etc. Specific examples include methyl, ethyl, n-propyl,
n-butyl, n-hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl,
amino-methyl, aminoethyl, aminopropyl, 2-ethylpyridine,
1-ethylpyrrolidine, 1-ethylpiperidine, etc.
[0107] The alkyl group can be an alkylene group containing from 1
to about 10 carbon atoms. Examples of such alkylene groups include,
methylene, ethylene, propylene, etc. Also are hydrocarbylene
groups, and in particular, alkylene group containing up to about 10
carbon atoms. Examples of such hydrocarbylene groups include,
methylene, ethylene, propylene, etc. The amide contains at least
one morpholinyl group. In one embodiment, the morpholine structure
is formed as a result of the condensation of two hydroxy groups
which are attached to the hydrocarbylene groups. Typically, the
amides are prepared by reacting a carboxylic acid or reactive
derivative thereof with an amine which contains at least one >NH
group.
[0108] Aliphatic monoamines include mono-aliphatic and
di-aliphatic-substituted amines wherein the aliphatic groups may be
saturated or unsaturated and straight chain or branched chain. Such
amines include, for example, mono- and di-alkyl-substituted amines,
mono- and dialkenyl-substituted amines, etc. Specific examples of
such monoamines include ethyl amine, diethyl amine, n-butyl amine,
di-n-butyl amine, isobutyl amine, coco amine, stearyl amine, oleyl
amine, etc. An example of a cycloaliphatic-substituted aliphatic
amine is 2-(cyclohexyl)-ethyl amine. Examples of
heterocyclic-substituted aliphatic amines include
2-(2-aminoethyl)-pyrrole, 2-(2-aminoethyl)-1-methylpyrrole,
2-(2-aminoethyl)-1-methylpyrrolidine and
4-(2-aminoethyl)morpholine, 1-(2-aminoethyl)piperazine,
1-(2-aminoethyl)piperidine, 2-(2-aminoethyl)pyridine,
1-(2-aminoethyl)pyrrolidine, 1-(3-aminopropyl)imidazole,
3-(2-aminopropyl)indole, 4-(3-aminopropyl)morpholine,
1-(3-aminopropyl)-2-pipecoline, 1-(3-aminopropyl)-2-pyrrolidinone,
etc.
[0109] Cycloaliphatic monoamines are those monoamines wherein there
is one cycloaliphatic substituent attached directly to the amino
nitrogen through a carbon atom in the cyclic ring structure.
Examples of cycloaliphatic monoamines include cyclohexylamines,
cyclopentylamines, cyclohexenylamines, cyclopentenylamines,
N-ethyl-cyclohexylamine, dicyclohexylamines, and the like. Examples
of aliphatic-substituted, aromatic-substituted, and
heterocyclic-substituted cycloaliphatic monoamines include
propyl-substituted cyclohexyl-amines, phenyl-substituted
cyclopentylamines, and pyranyl-substituted cyclohexylamine.
[0110] Aromatic amines include those monoamines wherein a carbon
atom of the aromatic ring structure is attached directly to the
amino nitrogen. The aromatic ring will usually be a mononuclear
aromatic ring (i.e., one derived from benzene) but can include
fused aromatic rings, especially those derived from naphthalene.
Examples of aromatic monoamines include aniline,
di-(para-methylphenyl)amine, naphthylamine, N-(n-butyl)-aniline,
and the like. Examples of aliphatic-substituted,
cycloaliphatic-substituted, and heterocyclic-substituted aromatic
monoamines are para-ethoxy-aniline, para-dodecylaniline,
cyclohexyl-substituted naphthylamine, variously substituted
phenathiazines, and thienyl-substituted aniline.
[0111] Polyamines are aliphatic, cycloaliphatic and aromatic
polyamines analogous to the above-described monoamines except for
the presence within their structure of additional amino nitrogens.
The additional amino nitrogens can be primary, secondary or
tertiary amino nitrogens. Examples of such polyamines include
N-amino-propyl-cyclohexylamines, N,N'-di-n-butyl-paraphenylene
diamine, bis-(para-aminophenyl)methane, 1,4-diaminocyclohexane, and
the like.
[0112] The hydroxy-substituted amines contemplated are those having
hydroxy substituents bonded directly to a carbon atom other than a
carbonyl carbon atom; that is, they have hydroxy groups capable of
functioning as alcohols. Examples of such hydroxy-substituted
amines include ethanolamine, di-(3-hydroxypropyl)-amine,
3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanolamine,
di-(2-hydroxyamine, N-(hydroxypropyl)-propylamine,
N-(2-methyl)-cyclohexylamine, 3-hydroxycyclopentyl
parahydroxyaniline, N-hydroxyethal piperazine and the like.
[0113] In one embodiment, the amines useful in the present
invention are alkylene polyamines including hydrogen, or a
hydrocarbyl, amino hydrocarbyl, hydroxyhydrocarbyl or
heterocyclic-substituted hydrocarbyl group containing up to about
10 carbon atoms, Alk is an alkylene group containing up to about 10
carbon atoms, and is 2 to about 10. Preferably, Alk is ethylene or
propylene. Usually, a will have an average value of from 2 to about
7. Examples of such alkylene polyamines include methylene
polyamines, ethylene polyamines, butylene polyamines, propylene
polyamines, pentylene polyamines, hexylene polyamines, heptylene
polyamines, etc.
[0114] Alkylene polyamines include ethylene diamine, triethylene
tetramine, propylene diamine, trimethylene diamine, hexamethylene
diamine, decamethylene diamine, hexamethylene diamine,
decamethylene diamine, octamethylene diamine, di(heptamethylene)
triamine, tripropylene tetramine, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine,
di(trimethylene)triamine, and the like. Higher homologs as are
obtained by condensing two or more of the above-illustrated
alkylene amines are useful, as are mixtures of two or more of any
of the afore-described polyamines.
[0115] Ethylene polyamines, such as those mentioned above, are
especially useful for reasons of cost and effectiveness. Such
polyamines are described in detail under the heading "Diamines and
Higher Amines" in The Encyclopedia of Chemical Technology, Second
Edition, Kirk and Othmer, Volume 7, pages 27-39, Interscience
Publishers, Division of John Wiley and Sons, 1965, which is hereby
incorporated by reference for the disclosure of useful polyamines.
Such compounds are prepared most conveniently by the reaction of an
alkylene chloride with ammonia or by reaction of an ethylene imine
with a ring-opening reagent such as ammonia, etc. These reactions
result in the production of the somewhat complex mixtures of
alkylene polyamines, including cyclic condensation products such as
piperazines.
[0116] Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mixtures. In this
instance, lower molecular weight polyamines and volatile
contaminants are removed from an alkylene polyamine mixture to
leave as residue what is often termed "polyamine bottoms". In
general, alkylene polyamine bottoms can be characterized as having
less than 2, usually less than 1% (by weight) material boiling
below about 200.degree. C. In the instance of ethylene polyamine
bottoms, which are readily available and found to be quite useful,
the bottoms contain less than about 2% (by weight) total diethylene
triamine (DETA) or triethylene tetramine (TETA). A typical sample
of such ethylene polyamine bottoms obtained from the Dow Chemical
Company of Freeport, Tex. designated "E-100". Gas chromatography
analysis of such a sample showed it to contain about 0.93% "Light
Ends" (most probably DETA), 0.72% TETA, 21.74% tetraethylene
pentamine and 76.61% pentaethylene hexamine and higher (by weight).
These alkylene polyamine bottoms include cyclic condensation
products such as piperazine and higher analogs of diethylene
triamine, triethylene tetramine and the like.
[0117] The dispersants are selected from:
[0118] Mannich bases that are condensation reaction products of a
high molecular weight phenol, an alkylene polyamine and an aldehyde
such as formaldehyde, Succinic-based dispersants that are reaction
products of a olefin polymer and succinic acylating agent (acid,
anhydride, ester or halide) further reacted with an organic hydroxy
compound and/or an amine, High molecular weight amides and esters
such as reaction products of a hydrocarbyl acylating agent and a
polyhydric aliphatic alcohol (such as glycerol, pentaerythritol or
sorbitol). Ashless (metal-free) polymeric materials that usually
contain an oil soluble high molecular weight backbone linked to a
polar functional group that associates with particles to be
dispersed are typically used as dispersants. Zinc acetate capped,
also any treated dispersant, which include borated, cyclic
carbonate, end-capped, polyalkylene maleic anhydride and the like;
mixtures of some of the above, in treat rates that range from about
0.1% up to 10-20% or more. Commonly used hydrocarbon backbone
materials are olefin polymers and copolymers, i.e.--ethylene,
propylene, butylene, isobutylene, styrene; there may or may not be
further functional groups incorporated into the backbone of the
polymer, whose molecular weight ranges from 300 tp to 5000. Polar
materials such as amines, alcohols, amides or esters are attached
to the backbone via a bridge.
[0119] Antioxidants include sterically hindered alkyl phenols such
as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and
2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol;
N,N-di(alkylphenyl) amines; and alkylated phenylene-diamines.
[0120] The antioxidant component may be a hindered phenolic
antioxidant such as butylated hydroxytoluene, suitably present in
an amount of 0.01 to 5%, preferably 0.4 to 0.8%, by weight of the
lubricant composition. Alternatively, or in addition, component b)
may comprise an aromatic amine antioxidant such as
mono-octylphenylalphanapthylamine or p,p-dioctyldiphenylamine, used
singly or in admixture. The amine anti-oxidant component is
suitably present in a range of from 0.01 to 5% by weight of the
lubricant composition, more preferably 0.5 to 1.5%.
[0121] A sulfur-containing antioxidant may be any and every
antioxidant containing sulfur, for example, including dialkyl
thiodipropionates such as dilauryl thiodipropionate and distearyl
thiodipropionate, dialkyldithiocarbamic acid derivatives (excluding
metal salts), bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide,
mercaptobenzothiazole, reaction products of phosphorus pentoxide
and olefins, and dicetyl sulfide. Of these, preferred are dialkyl
thiodipropionates such as dilauryl thiodipropionate and distearyl
thiodipropionate. The amine-type antioxidant includes, for example,
monoalkyldiphenylamines such as monooctyldiphenylamine and
monononyldiphenylamine; dialkyldiphenylamines such as
4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine,
4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine,
4,4'-dioctyldiphenylamine and 4,4'-dinonyldiphenylamine,
polyalkyldiphenylamines such as tetrabutyldiphenylamine,
tetrahexyldiphenylamine, tetraoctyldiphenylamine and
tetranonyldiphenylamine; and naphthylamines such as
.alpha.-naphthylamine, phenyl-.alpha.-naphthylamine,
butylphenyl-.alpha.-naphthylamine,
pentylphenyl-.alpha.-naphthylamine,
hexylphenyl-.alpha.-naphthylamine,
heptylphenyl-.alpha.-naphthylamine,
octylphenyl-.alpha.-naphthylamine and
nonylphenyl-.alpha.-naphthylamine. Of these, preferred are
dialkyldiphenylamines. The sulfur-containing antioxidant and the
amine-type antioxidant are added to the base oil in an amount of
from 0.01 to 5% by weight, preferably from 0.03 to 3% by weight,
relative to the total weight of the composition.
[0122] The oxidation inhibitors that are particularly useful in
lube compositions of the invention are the hindered phenols (e.g.,
2,6-di-(t-butyl)phenol); aromatic amines (e.g., alkylated diphenyl
amines); alkyl polysulfides; selenides; borates (e.g.,
epoxide/boric acid reaction products); phosphorodithioic acids,
esters and/or salts; and the dithiocarbamate (e.g., zinc
dithiocarbamates). These oxidation inhibitors as well as the
oxidation inhibitors discussed above the preferably of the
invention at levels of about 0.05% to about 5%, more preferably
about 0.25 to about 2% by weight based on the total weight of such
compositions; with ratios of amine/phenolic to be from 1:10 to 10:1
of the mixtures preferred.
[0123] The oxidation inhibitors that are also useful in lube
compositions of the invention are chlorinated aliphatic
hydrocarbons such as chlorinated wax; organic sulfides and
polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide,
dibutyl tetrasulfide, sulfurized methyl ester of oleic acid,
sulfurized alkylphenol, sulfurized dipentene, and sulfurized
terpene; phosphosulfurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl oleate,
phosphorus esters including principally dihydrocarbon and
trihydrocarbon phosphites such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,
dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl phosphite,
diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such
as zinc dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,
barium di(heptylphenyl)(phosphorodithioate, cadmium
dinonylphosphorodithioate, and the reaction of phosphorus
pentasulfide with an equimolar mixture of isopropyl alcohol,
4-methyl-2-pentanol, and n-hexyl alcohol.
[0124] Oxidation inhibitors, organic compounds containing sulfur,
nitrogen, phosphorus and some alkylphenols are also employed. Two
general types of oxidation inhibitors are those that react with the
initiators, peroxy radicals, and hydroperoxides to form inactive
compounds, and those that decompose these materials to form less
active compounds. Examples are hindered (alkylated) phenols, e.g.
6-di(tert-butyl)-4-methylphenol [2,6-di(tert-butyl)-p-cresol,
DBPC], and aromatic amines, e.g. N-phenyl-.alpha.-naphthalamine.
These are used in turbine, circulation, and hydraulic oils that are
intended for extended service.
[0125] Examples of amine-based antioxidants include
dialkyldiphenylamines such as p,p'-dioctyldiphenylamine
(manufactured by the Seiko Kagaku Co. under the trade designation
"Nonflex OD-3"), p,p'-di-.alpha.-methylbenzyl-diphenylamine and
N-p-butylphenyl-N-p'-octylphenylamine; monoalkyldiphenylamines such
as mono-t-butyldiphenylamine, and monooctyldiphenylamine;
bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and
di(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines such
as octylphenyl-1-naphthylamine and
N-t-dodecylphenyl-1-naphthylamine; arylnaphthylamines such as
1-naphthylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine,
N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine,
phenylenediamines such as N,N'-diisopropyl-p-phenylenediamine and
N,N'-diphenyl-p-phenylenediamine, and phenothiazines such as
phenothiazine (manufactured by the Hodogaya Kagaku Co.:
Phenothiazine) and 3,7-dioctylphenothiazine.
[0126] Examples of sulphur-based antioxidants include
dialkylsulphides such as didodecylsulphide and dioctadecylsulphide;
thiodipropionic acid esters such as didodecyl thiodipropionate,
dioctadecyl thiodipropionate, dimyristyl thiodipropionate and
dodecyloctadecyl thiodipropionate, and 2-mercaptobenzimidazole.
[0127] Examples of phenol-based antioxidants include
2-t-butylphenol, 2-t-butyl-4-methylphenol,
2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol,
2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (manufactured
by the Kawaguchi Kagaku Co. under trade designation "Antage DBH"),
2,6-di-t-butylphenol and 2,6-di-t-butyl-4-alkylphenols such as
2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol;
2,6-di-t-butyl-4-alkoxyphenols such as
2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,
3,5-di-t-butyl-4-hydroxybenzylmercaptoocty-1 acetate,
alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such as
n-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yonox
SS"), n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol,
2,2'-methylenebis(4-alkyl--6-t-butylphenol) compounds such as
2,2'-methylenebis(4-methyl-6-t-butylphe-nol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-400")
and 2,2'-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-500");
bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butyl-phenol)
(manufactured by the Kawaguchi Kagaku Co. under the trade
designation "Antage W-300"),
4,4'-methylenebis(2,6-di-t-butylphenol) (manufactured by Laporte
Performance Chemicals under the trade designation "Ionox 220AH"),
4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane
(Bisphenol A), 2,2-bis(3,5-di-t-butyl-4-h-ydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycol
bis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate](manufactured by
the Ciba Speciality Chemicals Co. under the trade designation
"Irganox L109"), triethylene glycol
bis[3-(3-t-butyl-4-hydrox-y-5-methylphenyl)propionate]
(manufactured by the Yoshitomi Seiyaku Co. under the trade
designation "Tominox 917"),
2,2'-thio[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
(manufactured by the Ciba Speciality Chemicals Co. under the trade
designation "Irganox L115"),
3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionylo-
-xy]ethyl}2,4,8,10-tetraoxaspiro[5,5]undecane (manufactured by the
Sumitomo Kagaku Co. under the trade designation "Sumilizer GA80")
and 4,4'-thiobis(3-methyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage RC"),
2,2'-thiobis(4,6-di-t-butylresorcinol); polyphenols such as
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionato]methane
(manufactured by the Ciba Speciality Chemicals Co. under the trade
designation "Irganox L101"),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylpheny-1)butane (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yoshinox
930"),
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene
(manufactured by Ciba Speciality Chemicals under the trade
designation "Irganox 330"),
bis[3,3'-bis(4'-hydroxy-3'-t-butylpheny-1)butyric acid] glycol
ester,
2-(3',5'-di-t-butyl-4-hydroxyphenyl)-methyl--4-(2'',4''-di-t-butyl-3''-hy-
droxyphenyl)methyl-6-t-butylphenol and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol; and
phenol/aldehyde condensates such as the condensates of
p-t-butylphenol and formaldehyde and the condensates of
p-t-butylphenol and acetaldehyde.
[0128] Viscosity index improvers and/or the pour point depressant
include polymeric alkylmethacrylates and olefinic copolymers such
as an ethylene-propylene copolymer or a styrene-butadiene copolymer
or polyalkene such as PIB. Viscosity index improvers (VI
improvers), high molecular weight polymers that increase the
relative viscosity of an oil at high temperatures more than they do
at low temperatures. The most common VI improvers are methacrylate
polymers and copolymers, acrylate polymers, olefin polymers and
copolymers, and styrene-butadiene copolymers.
[0129] Other examples of the viscosity index improver include
polymethacrylate, polyisobutylene, alpha-olefin polymers,
alpha-olefin copolymers (e.g., an ethylene-propylene copolymer),
polyalkylstyrene, phenol condensates, naphthalene condensates, a
styrenebutadiene copolymer and the like. Of these, polymethacrylate
having a number average molecular weight of 10,000 to 300,000, and
alpha-olefin polymers or alpha-olefin copolymers having a number
average molecular weight of 1,000 to 30,000, particularly
ethylene-alpha-olefin copolymers having a number average molecular
weight of 1,000 to 10,000 are preferred.
[0130] The viscosity index increasing agents which can be used
include, for example, polymethacrylates and ethylene/propylene
copolymers, other non-dispersion type viscosity index increasing
agents such as olefin copolymers like styrene/diene copolymers, and
dispersible type viscosity index increasing agents where a nitrogen
containing monomer has been copolymerized in such materials. These
materials can be added and used individually or in the form of
mixtures, conveniently in an amount within the range of from 0.05
to 20 parts by weight per 100 parts by weight of base oil.
[0131] Pour point depressors (PPD) include polymethacrylates.
Commonly used additives such as alkylaromatic polymers and
polymethacrylates are useful for this purpose; typically the treat
rates range from 0.001% to 1.0%.
[0132] Detergents include calcium alkylsalicylates, calcium
alkylphenates and calcium alkarylsulfonates with alternate metal
ions used such as magnesium, barium, or sodium. Examples of the
cleaning and dispersing agents which can be used include
metal-based detergents such as the neutral and basic alkaline earth
metal sulphonates, alkaline earth metal phenates and alkaline earth
metal salicylates alkenylsuccinimide and alkenylsuccinimide esters
and their borohydrides, phenates, salienius complex detergents and
ashless dispersing agents which have been modified with sulphur
compounds. These agents can be added and used individually or in
the form of mixtures, conveniently in an amount within the range of
from 0.01 to 1 part by weight per 100 parts by weight of base oil;
these can also be high TBN, low TBN, or mixtures of high/low
TBN.
[0133] Anti-rust additives include (short-chain) alkenyl succinic
acids, partial esters thereof and nitrogen-containing derivatives
thereof; and synthetic alkarylsulfonates, such as metal
dinonylnaphthalene sulfonates. Anti-rust agents include, for
example, monocarboxylic acids which have from 8 to 30 carbon atoms,
alkyl or alkenyl succinates or partial esters thereof,
hydroxy-fatty acids which have from 12 to 30 carbon atoms and
derivatives thereof, sarcosines which have from 8 to 24 carbon
atoms and derivatives thereof, amino acids and derivatives thereof,
naphthenic acid and derivatives thereof, lanolin fatty acid,
mercapto-fatty acids and paraffin oxides.
[0134] Particularly preferred anti-rust agents are indicated below.
Examples of Monocarboxylic Acids (C8-C30), Caprylic acid,
pelargonic acid, decanoic acid, undecanoic acid, lauric acid,
myristic acid, palmitic acid, stearic acid, arachic acid, behenic
acid, cerotic acid, montanic acid, melissic acid, oleic acid,
docosanic acid, erucic acid, eicosenic acid, beef tallow fatty
acid, soy bean fatty acid, coconut oil fatty acid, linolic acid,
linoleic acid, tall oil fatty acid, 12-hydroxystearic acid,
laurylsarcosinic acid, myritsylsarcosinic acid, palmitylsarcosinic
acid, stearylsarcosinic acid, oleylsarcosinic acid, alkylated
(C8-C20) phenoxyacetic acids, lanolin fatty acid and C8-C24
mercapto-fatty acids.
[0135] Examples of Polybasic Carboxylic Acids: The alkenyl
(C10--C100) succinic acids indicated in CAS No. 27859-58-1 and
ester derivatives thereof, dimer acid, N-acyl-N-alkyloxyalkyl
aspartic acid esters (U.S. Pat. No. 5,275,749). Examples of the
alkylamines which function as antirust additives or as reaction
products with the above carboxylates to give amides and the like
are represented by primary amines such as laurylamine,
coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine,
palmitylamine, n-heptadecylamine, stearylamine, n-nonadecylamine,
n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine,
n-pentacosylamine, oleylamine, beef tallow-amine, hydrogenated beef
tallow-amine and soy bean-amine. Examples of the secondary amines
include dilaurylamine, di-coconut-amine, di-n-tridecylamine,
dimyristylamine, di-n-pentadecylamine, dipalmitylamine,
di-n-pentadecylamine, distearylamine, di-n-nonadecylamine,
di-n-eicosylamine, di-n-heneicosylamine, di-n-docosylamine,
di-n-tricosylamine, di-n-pentacosyl-amine, dioleylamine, di-beef
tallow-amine, di-hydrogenated beef tallow-amine and di-soy
bean-amine. Examples of the aforementioned
N-alkylpolyalkyenediamines include: ethylenediamines such as
laurylethylenediamine, coconut ethylenediamine,
n-tridecylethylenediamine-, myristylethylenediamine,
n-pentadecylethylenediamine, palmitylethylenediamine,
n-heptadecylethylenediamine, stearylethylenediamine,
n-nonadecylethylenediamine, n-eicosylethylenediamine,
n-heneicosylethylenediamine, n-docosylethylendiamine,
n-tricosylethylenediamine, n-pentacosylethylenediamine,
oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated
beef tallow-ethylenediamine and soy bean-ethylenediamine;
propylenediamines such as laurylpropylenediamine, coconut
propylenediamine, n-tridecylpropylenediamine,
myristylpropylenediamine, n-pentadecylpropylenediamine,
palmitylpropylenediamine, n-heptadecylpropylenediamine,
stearylpropylenediamine, n-nonadecylpropylenediamine,
n-eicosylpropylenediamine, n-heneicosylpropylenediamine,
n-docosylpropylendiamine, n-tricosylpropylenediamine,
n-pentacosylpropylenediamine, diethylene triamine (DETA) or
triethylene tetramine (TETA), oleylpropylenediamine, beef
tallow-propylenediamine, hydrogenated beef tallow-propylenediamine
and soy bean-propylenediamine; butylenediamines such as
laurylbutylenediamine, coconut butylenediamine,
n-tridecylbutylenediamine-, myristylbutylenediamine,
n-pentadecylbutylenediamine, stearylbutylenediamine,
n-eicosylbutylenediamine, n-heneicosylbutylenedia-mine,
n-docosylbutylendiamine, n-tricosylbutylenediamine,
n-pentacosylbutylenediamine, oleylbutylenediamine, beef
tallow-butylenediamine, hydrogenated beef tallow-butylenediamine
and soy bean butylenediamine; and pentylenediamines such as
laurylpentylenediamine, coconut pentylenediamine,
myristylpentylenediamin-e, palmitylpentylenediamine,
stearylpentylenediamine, oleyl-pentylenediamine, beef
tallow-pentylenediamine, hydrogenated beef tallow-pentylenediamine
and soy bean pentylenediamine.
[0136] Demulsifying agents include alkoxylated phenols and
phenol-formaldehyde resins and synthetic alkylaryl sulfonates such
as metallic dinonylnaphthalene sulfonates. A demulsifing agent is a
predominant amount of a water-soluble polyoxyalkylene glycol having
a pre-selected molecular weight of any value in the range of
between about 450 and 5000 or more. An especially preferred family
of water soluble polyoxyalkylene glycol useful in the compositions
of the present invention may also be one produced from alkoxylation
of n-butanol with a mixture of alkylene oxides to form a random
alkoxylated product.
[0137] Functional fluids according to the invention possess a pour
point of less than about -20 degree C., and exhibit compatibility
with a wide range of anti-wear additive and extreme pressure
additives. The formulations according to the invention also are
devoid of fatigue failure that is normally expected by those of
ordinary skill in the art when dealing with polar lubricant base
stocks.
[0138] Polyoxyalkylene glycols useful in the present invention may
be produced by a well-known process for preparing polyalkylene
oxide having hydroxyl end-groups by subjecting an alcohol or a
glycol ether and one or more alkylene oxide monomers such as
ethylene oxide, butylene oxide, or propylene oxide to form block
copolymers in addition polymerization while employing a strong base
such as potassium hydroxide as a catalyst. In such process, the
polymerization is commonly carried out under a catalytic
concentration of 0.3 to 1.0% by mole of potassium hydroxide to the
monomer(s) and at high temperature, as 100 degrees C. to 160
degrees C. It is well known fact that the potassium hydroxide being
a catalyst is for the most part bonded to the chain-end of the
produced polyalkylene oxide in a form of alkoxide in the polymer
solution so obtained.
[0139] An especially preferred family of soluble polyoxyalkylene
glycol useful in the compositions of the present invention may also
be one produced from alkoxylation of n-butanol with a mixture of
alkylene oxides to form a random alkoxylated product.
[0140] Foam inhibitors include polymers of alkyl methacrylate
especially useful poly alkyl acrylate polymers where alkyl is
generally understood to be methyl, ethyl propyl, isopropyl, butyl,
or iso butyl and polymers of dimethylsilicone which form materials
called dimethylsiloxane polymers in the viscosity range of 10 cSt
to 100,000 cSt. Other additives are defoamers, such as silicone
polymers which have been post reacted with various carbon
containing moieties, are the most widely used defoamers. Organic
polymers are sometimes used as defoamers although much higher
concentrations are required.
[0141] Metal deactivating compounds/Corrosion inhibitors include
2,5-dimercapto-1,3,4-thiadiazoles and derivatives thereof,
mercaptobenzothiazoles, alkyltriazoles and benzotriazoles. Examples
of dibasic acids useful as anti-corrosion agents, other than
sebacic acids, which may be used in the present invention, are
adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid,
3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and fumaric
acid. The anti-corrosion combination is a straight or
branch-chained, saturated or unsaturated monocarboxylic acid or
ester thereof which may optionally be sulphurised in an amount up
to 35% by weight. Preferably the acid is a C sub 4 to C sub 22
straight chain unsaturated monocarboxylic acid. The preferred
concentration of this additive is from 0.001% to 0.35% by weight of
the total lubricant composition. The preferred monocarboxylic acid
is sulphurised oleic acid. However, other suitable materials are
oleic acid itself; valeric acid and erucic acid. A component of the
anti-corrosion combination is a triazole as previously defined. The
triazole should be used at a concentration from 0.005% to 0.25% by
weight of the total composition. The preferred triazole is
tolylotriazole which may be included in the compositions of the
invention include triazoles, thiazoles and certain diamine
compounds which are useful as metal deactivators or metal
passivators. Examples include triazole, benzotriazole and
substituted benzotriazoles such as alkyl substituted derivatives.
The alkyl substituent generally contains up to 1.5 carbon atoms,
preferably up to 8 carbon atoms. The triazoles may contain other
substituents on the aromatic ring such as halogens, nitro, amino,
mercapto, etc. Examples of suitable compounds are benzotriazole and
the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles,
octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles.
Benzotriazole and tolyltriazole are particularly preferred. A
straight or branched chain saturated or unsaturated monocarboxylic
acid which is optionally sulphurised in an amount which may be up
to 35% by weight; or an ester of such an acid; and a triazole or
alkyl derivatives thereof, or short chain alkyl of up to 5 carbon
atoms; n is zero or an integer between 1 and 3 inclusive; and is
hydrogen, morpholino, alkyl, amido, amino, hydroxy or alkyl or aryl
substituted derivatives thereof; or a triazole selected from 1,2,4
triazole, 1,2,3 triazole, 5-anilo-1,2,3,4-thiatriazole,
3-amino-1,2,4 triazole, 1-H-benzotriazole-1-yl-methylisocyanide,
methylene-bis-benzotriazole and naphthotriazole.
[0142] Alkyl is straight or branched chain and is for example
methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl,
n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.
[0143] Alkenyl is straight or branched chain and is for example
prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl,
hexa-2,4-dienyl, dec-10-enyl or eicos-2-enyl.
[0144] Cylcoalkyl is for example cyclopentyl, cyclohexyl,
cyclooctyl, cyclodecyl, adamantyl or cyclododecyl.
[0145] Aralkyl is for example benzyl, 2-phenylethyl, benzhydryl or
naphthylmethyl. Aryl is for example phenyl or naphthyl.
[0146] The heterocyclic group is for example a morpholine,
pyrrolidine, piperidine or a perhydroazepine ring.
[0147] Alkylene moieties include for example methylene, ethylene,
1:2- or 1:3-propylene, 1:4-butylene, 1:6-hexylene, 1:8-octylene,
1:10-decylene and 1:12-dodecylene.
[0148] Arylene moieties include for example phenylene and
naphthylene. 1-(or 4)-(dimethylaminomethyl) triazole, 1-(or
4)-(diethylaminomethyl) triazole, 1-(or
4)-(di-isopropylaminomethyl) triazole, 1-(or
4)-(di-n-butylaminomethyl) triazole, 1-(or
4)-(di-n-hexylaminomethyl) triazole, 1-(or
4)-(di-isooctylaminomethyl) triazole, 1-(or
4)-(di-(2-ethylhexyl)aminomethyl) triazole, 1-(or
4)-(di-n-decylaminomethyl) triazole, 1-(or
4)-(di-n-dodecylaminomethyl) triazole, 1-(or
4)-(di-n-octadecylaminomethyl) triazole, 1-(or
4)-(di-n-eicosylaminomethyl) triazole, 1-(or
4)-[di-(prop-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(but-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(eicos-2'-enyl)aminomethyl] triazole, 1-(or
4)-(di-cyclohexylaminomethyl) triazole, 1-(or
4)-(di-benzylaminomethyl) triazole, 1-(or 4)-(di-phenylaminomethyl)
triazole, 1-(or 4)-(4'-morpholinomethyl) triazole, 1-(or
4)-(1'-pyrrolidinomethyl) triazole, 1-(or 4)-(1'-piperidinomethyl)
triazole, 1-(or 4)-(1'-perhydroroazepinomethyl) triazole, 1-(or
4)-(2',2''-dihydroxyethyl)aminomethyl] triazole, 1-(or
4)-(dibutoxypropyl-aminomethyl) triazole, 1-(or
4)-(dibutylthiopropyl-aminomethyl) triazole, 1-(or
4)-(di-butylaminopropyl-aminomethyl) triazole, 1-(or
-4)-(1-methanomine)-N,N-bis(2-ethylhexyl)-methyl benzotriazole,
N,N-bis-(1- or 4-triazolylmethyl) laurylamine, N,N-bis-(1- or
4-triazolylmethyl) oleylamine, N,N-bis-(1- or
4-triazolylmethyl)ethanolamine and N,N,N',N'-tetra(1- or
4-triazolylmethyl)ethylene diamine.
[0149] Also, dihydrocarbyl dithiophosphate metal salts where the
metal is aluminum, lead, tin, manganese, molybedenum, antimony,
cobalt, nickel, zinc or copper, but most often zinc. Sulfur- and/or
phosphorus- and/or halogen-containing compounds, such as sulfurized
olefins and vegetable oils, tritolyl phosphate, tricresyl
phosphate, chlorinated paraffins, alkyl and aryl di- and
trisulfides, amine salts of mono- and dialkyl phosphates, amine
salts of methylphosphonic acid, diethanolaminomethyltolyltriazole,
di(2-ethylhexyl)-aminomethyltolyltriazole, derivatives of
2,5-dimercapto-1,3,4-thiadiazole, ethyl
((bisisopropyloxyphosphinothioyl)-thio)propionate, triphenyl
thiophosphate (triphenyl phosphorothioate), tris(alkylphenyl)
phosphorothioates and mixtures thereof (for example
tris(isononylphenyl) phosphorothioate), diphenylmonononylphenyl
phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the
dodecylamine salt of 3-hydroxy-1,3-thiaphosphetan 3-oxide,
trithiophosphoric acid 5,5,5-tris(isooctyl 2-acetate), derivatives
of 2-mercaptobenzothiazole, such as
1-(N,N-bis(2-ethylhexyl)aminomethyl)-2-m-ercapto-1H-1,3-benzothia-
zole or ethoxycarbonyl 5-octyldithiocarbamate.
[0150] The metal deactivating agents which can be used in the
lubricating oil a composition of the present invention include
benzotriazole and the 4-alkylbenzotriazoles such as
4-methylbenzotriazole and 4-ethylbenzotriazole;
5-alkylbenzotriazoles such as 5-methylbenzotriazole,
5-ethylbenzotriazole; 1-alkylbenzotriazoles such as
1-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivatives
such as the 1-alkyltolutriazoles, for example,
1-dioctylaminomethyl-2,3-t-olutriazole; benzimidazole and
benzimidazole derivatives such as 2-(alkyldithio)-benzimidazoles,
for example, such as 2-(octyldithio)-benzimidazole,
2-(decyldithio)benzimidazole and 2-(dodecyldithio)-benzimidazole;
2-(alkyldithio)-toluimidazoles such as
2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole and
2-(dodecyldithio)-toluimidazole; indazole and indazole derivatives
of toluimidazoles such as 4-alkylindazole, 5-alkylindazole;
benzothiazole, 2-mercaptobenzothiazole derivatives (manufactured by
the Chiyoda Kagaku Co. under the trade designation "Thiolite
B-3100") and 2-(alkyldithio)benzothiazoles such as
2-(hexyldithio)benzothiazole and 2-(octyldithio)benzothiazole;
2-(alkyl-dithio)toluthiazoles such as 2-(benzyldithio)toluthiazole
and 2-(octyldithio)toluthiazole,
2-(N,N-dialkyldithiocarbamyl)benzothiazoles such as
2-(N,N-diethyldithiocarbamyl)benzothiazole,
2-(N,N-dibutyldithiocarbamyl)-benzotriazole and
2-N,N-dihexyl-dithiocarbamyl)benzotriazole; benzothiazole
derivatives of 2-(N,N-dialkyldithiocarbamyl)toluthiazoles such as
2-(N,N-diethyldithiocarbamyl)toluthiazole,
2-(N,N-dibutyldithiocarbamyl)toluthiazole,
2-(N,N-dihexyl-dithiocarbamyl)-toluthiazole;
2-(alkyldithio)benzoxazoles such as 2-(octyldithio)benzoxazo-le,
2-(decyldithio)-benzoxazole and 2-(dodecyldithio)benzoxazole;
benzoxazole derivatives of 2-(alkyldithio)toluoxazoles such as
2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole,
2-(dodecyldithio)toluoxazole;
2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as
2,5-bis(heptyldithio)-1,3,4-thiadiazole, 2,5-bis-(nonyldithio)-1,
-3,4-thiadiazole, 2,5-bis(dodecyldithio)-1,3,4-thiadiazole and
2,5-bis-(octadecyldithio)-1,3,4-thiadiazole;
2,5-bis(N,N-dialkyl-dithiocarbamyl)-1,3,4-thiadiazoles such as
2,5-bis(N,N-diethyldithiocarbamyl)-1,3,-4-thiadiazole,
2,5-bis(N,N-dibutyldithiocarbamyl)-1,3,4-thiadiazole and
2,5-bis(N,N-dioctyldithiocarbamyl)1,3,4-thiadiazole; thiadiazole
derivatives of
2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazoles such as
2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole and
2-N,N-dioctyl-dithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and
triazole derivatives of 1-alkyl-2,4-triazoles such as
1-dioctylaminomethyl-2,4-tri-azole or concentrates and/or mixtures
thereof.
[0151] Anti-wear agents/Extreme pressure agent/Friction Reducer:
zinc alkyldithiophosphates, aryl phosphates and phosphites,
sulfur-containing esters, phosphosulfur compounds, and metal or
ash-free dithiocarbamates.
[0152] A phosphate ester or salt may be a monohydrocarbyl,
dihydrocarbyl or a trihydrocarbyl phosphate, wherein each
hydrocarbyl group is saturated. In one embodiment, each hydrocarbyl
group independently contains from about 8 to about 30, or from
about 12 up to about 28, or from about 14 up to about 24, or from
about 14 up to about 18 carbons atoms. In one embodiment, the
hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups
include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl groups and mixtures thereof.
[0153] A phosphate ester or salt is a phosphorus acid ester
prepared by reacting one or more phosphorus acid or anhydride with
a saturated alcohol. The phosphorus acid or anhydride is generally
an inorganic phosphorus reagent, such as phosphorus pentoxide,
phosphorus trioxide, phosphorus tetroxide, phosphorous acid,
phosphoric acid, phosphorus halide, lower phosphorus esters, or a
phosphorus sulfide, including phosphorus pentasulfide, and the
like. Lower phosphorus acid esters generally contain from 1 to
about 7 carbon atoms in each ester group. Alcohols used to prepare
the phosphorus acid esters or salts. Examples of commercially
available alcohols and alcohol mixtures include Alfol 1218 (a
mixture of synthetic, primary, straight-chain alcohols containing
12 to 18 carbon atoms); Alfol 20+ alcohols (mixtures of C 18-C 28
primary alcohols having mostly C20 alcohols as determined by GLC
(gas-liquid-chromatography)); and Alfol22+ alcohols (C 18-C 28
primary alcohols containing primarily C 22 alcohols). Alfol
alcohols are available from Continental Oil Company. Another
example of a commercially available alcohol mixture is Adol 60
(about 75% by weight of a straight chain C 22 primary alcohol,
about 15% of a C 20 primary alcohol and about 8% of C 18 and C 24
alcohols). The Adol alcohols are marketed by Ashland Chemical.
[0154] A variety of mixtures of monohydric fatty alcohols derived
from naturally occurring triglycerides and ranging in chain length
from C 8 to C 18 are available from Procter & Gamble Company.
These mixtures contain various amounts of fatty alcohols containing
12, 14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty
alcohol mixture containing 0.5% of C 10 alcohol, 66.0% of C 12
alcohol, 26.0% of C 14 alcohol and 6.5% of C 16 alcohol.
[0155] Another group of commercially available mixtures include the
"Neodol" products available from Shell Chemical Co. For example,
Neodol 23 is a mixture of C 12 and C 13 alcohols; Neodol 25 is a
mixture of C 12 to C 15 alcohols; and Neodol 45 is a mixture of C
14 to C 15 linear alcohols. The phosphate contains from about 14 to
about 18 carbon atoms in each hydrocarbyl group. The hydrocarbyl
groups of the phosphate are generally derived from a mixture of
fatty alcohols having from about 14 up to about 18 carbon atoms.
The hydrocarbyl phosphate may also be derived from a fatty vicinal
diol. Fatty vicinal diols include those available from Ashland Oil
under the general trade designation Adol 114 and Adol 158. The
former is derived from a straight chain alpha olefin fraction of C
11-C 14, and the latter is derived from a C 15-C 18 fraction.
[0156] The phosphate salts may be prepared by reacting an acidic
phosphate ester with an amine compound or a metallic base to form
an amine or a metal salt. The amines may be monoamines or
polyamines. Useful amines include those amines disclosed in U.S.
Pat. No. 4,234,435.
[0157] The monoamines generally contain a hydrocarbyl group which
contains from 1 to about 30 carbon atoms, or from 1 to about 12, or
from 1 to about 6. Examples of primary monoamines useful in the
present invention include methylamine, ethylamine, propylamine,
butylamine, cyclopentylamine, cyclohexylamine, octylamine,
dodecylamine, allylamine, cocoamine, stearylamine, and laurylamine.
Examples of secondary monoamines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, dicyclopentylamine,
dicyclohexylamine, methylbutylamine, ethylhexylamine, etc.
[0158] An amine is a fatty (C.sub.8-30) amine which includes
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,
n-hexadecylamine, n-octadecylamine, oleyamine, etc. Also useful
fatty amines include commercially available fatty amines such as
"Armeen" amines (products available from Akzo Chemicals, Chicago,
Ill.), such Armeen C, Armeen O, Armeen O L, Armeen T, Armeen H T,
Armeen S and Armeen S D, wherein the letter designation relates to
the fatty group, such as coco, oleyl, tallow, or stearyl
groups.
[0159] Other useful amines include primary ether amines, such as
those represented by the formula, R'' (OR')xNH 2, wherein R' is a
divalent alkylene group having about 2 to about 6 carbon atoms; x
is a number from one to about 150, or from about one to about five,
or one; and R'' is a hydrocarbyl group of about 5 to about 150
carbon atoms. An example of an ether amine is available under the
name SURFAM.RTM. amines produced and marketed by Mars Chemical
Company, Atlanta, Ga. Preferred etheramines are exemplified by
those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A
(linear C 16), SURFAM P17B (tridecyloxypropylamine). The carbon
chain lengths (i.e., C 14, etc.) of the SURFAMS described above and
used hereinafter are approximate and include the oxygen ether
linkage.
[0160] An amine is a tertiary-aliphatic primary amine. Generally,
the aliphatic group, preferably an alkyl group, contains from about
4 to about 30, or from about 6 to about 24, or from about 8 to
about 22 carbon atoms. Usually the tertiary alkyl primary amines
are monoamines the alkyl group is a hydrocarbyl group containing
from one to about 27 carbon atoms and R 6 is a hydrocarbyl group
containing from 1 to about 12 carbon atoms. Such amines are
illustrated by tert-butylamine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and
tert-octacosanylamine. Mixtures of tertiary aliphatic amines may
also be used in preparing the phosphate salt. Illustrative of amine
mixtures of this type are "Primene 81R" which is a mixture of C
11-C 14 tertiary alkyl primary amines and "Primene JMT" which is a
similar mixture of C 18-C 22 tertiary alkyl primary amines (both
are available from Rohm and Haas Company). The tertiary aliphatic
primary amines and methods for their preparation are known to those
of ordinary skill in the art. The tertiary aliphatic primary amine
useful for the purposes of this invention and methods for their
preparation are described in U.S. patent. An amine is a
heterocyclic polyamine. The heterocyclic polyamines include
aziridines, azetidines, azolidines, tetra- and dihydropyridines,
pyrroles, indoles, piperidines, imidazoles, di- and
tetra-hydroimidazoles, piperazines, isoindoles, purines,
morpholines, thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkyl-piperazines,
N,N'-diaminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and perhydro derivatives of each of the
above and mixtures of two or more of these heterocyclic amines.
Preferred heterocyclic amines are the saturated 5- and 6-membered
heterocyclic amines containing only nitrogen, oxygen and/or sulfur
in the hetero ring, especially the piperidines, piperazines,
thiomorpholines, morpholines, pyrrolidines, and the like.
Piperidine, aminoalkyl substituted piperidines, piperazine,
aminoalkyl substituted piperazines, morpholine, aminoalkyl
substituted morpholines, pyrrolidine, and aminoalkyl-substituted
pyrrolidines, are especially preferred. Usually the aminoalkyl
substituents are substituted on a nitrogen atom forming part of the
hetero ring. Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are
also useful. Examples include N-(2-hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, parahydroxyaniline,
N-hydroxyethylpiperazine, and the like.
[0161] The metal salts of the phosphorus acid esters are prepared
by the reaction of a metal base with the acidic phosphorus ester.
The metal base may be any metal compound capable of forming a metal
salt. Examples of metal bases include metal oxides, hydroxides,
carbonates, sulfates, borates, or the like. The metals of the metal
base include Group IA, IIA, IB through VIIB, and VIII metals (CAS
version of the Periodic Table of the Elements). These metals
include the alkali metals, alkaline earth metals and transition
metals. In one embodiment, the metal is a Group IIA metal, such as
calcium or magnesium, Group IIB metal, such as zinc, or a Group
VIIB metal, such as manganese. Preferably, the metal is magnesium,
calcium, manganese or zinc. Examples of metal compounds which may
be reacted with the phosphorus acid include zinc hydroxide, zinc
oxide, copper hydroxide, copper oxide, etc.
[0162] Lubricating compositions also may include a fatty
imidazoline or a reaction product of a fatty carboxylic acid and at
least one polyamine. The fatty imidazoline has fatty substituents
containing from 8 to about 30, or from about 12 to about 24 carbon
atoms. The substituent may be saturated or unsaturated for example,
heptadeceneyl derived olyel groups, preferably saturated. In one
aspect, the fatty imidazoline may be prepared by reacting a fatty
carboxylic acid with a polyalkylenepolyamine, such as those
discussed above. The fatty carboxylic acids are generally mixtures
of straight and branched chain fatty carboxylic acids containing
about 8 to about 30 carbon atoms, or from about 12 to about 24, or
from about 16 to about 18. Carboxylic acids include the
polycarboxylic acids or carboxylic acids or anhydrides having from
2 to about 4 carbonyl groups, preferably 2. The polycarboxylic
acids include succinic acids and anhydrides and Diels-Alder
reaction products of unsaturated monocarboxylic acids with
unsaturated carboxylic acids (such as acrylic, methacrylic, maleic,
fumaric, crotonic and itaconic acids). Preferably, the fatty
carboxylic acids are fatty monocarboxylic acids, having from about
8 to about 30, preferably about 12 to about 24 carbon atoms, such
as octanoic, oleic, stearic, linoleic, dodecanoic, and tall oil
acids, preferably stearic acid. The fatty carboxylic acid is
reacted with at least one polyamine. The polyamines may be
aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of
the polyamines include alkylene polyamines and heterocyclic
polyamines.
[0163] Hydroxyalkyl groups are to be understood as meaning, for
example, monoethanolamine, diethanolamine or triethanolamine, and
the term amine also includes diamine. The amine used for the
neutralization depends on the phosphoric esters used. The EP
additive according to the invention has the following advantages:
It very high effectiveness when used in low concentrations and it
is free of chlorine. For the neutralization of the phosphoric
esters, the latter are taken and the corresponding amine slowly
added with stirring. The resulting heat of neutralization is
removed by cooling. The EP additive according to the invention can
be incorporated into the respective base liquid with the aid of
fatty substances (e.g. tall oil fatty acid, oleic acid, etc.) as
solubilizers. The base liquids used are napthenic or paraffinic
base oils, synthetic oils (e.g. polyglycols, mixed polyglycols),
polyolefins, carboxylic esters, etc.
[0164] The composition comprises at least one phosphorus containing
extreme pressure additive. Examples of such additives are amine
phosphate extreme pressure additives such as that known under the
trade name IRGALUBE 349 and/or triphenyl phosphorothionate extreme
pressure/anti-wear additives such as that known under the trade
name IRGALUBE TPPT. Such amine phosphates are suitably present in
an amount of from 0.01 to 2%, preferably 0.2 to 0.6% by weight of
the lubricant composition while such phosphorothionates are
suitably present in an amount of from 0.01 to 3%, preferably 0.5 to
1.5% by weight of the lubricant composition. A mixture of an amine
phosphate and phosphorothionate is employed.
[0165] At least one straight and/or branched chain saturated or
unsaturated monocarboxylic acid which is optionally sulphurised in
an amount which may be up to 35% by weight; and/or an ester of such
an acid. At least one triazole or alkyl derivatives thereof, or
short chain alkyl of up to 5 carbon atoms and is hydrogen,
morphilino, alkyl, amido, amino, hydroxy or alkyl or aryl
substituted derivatives thereof; or a triazole selected from 1,2,4
triazole, 1,2,3 triazole, 5-anilo-1,2,3,4-thiatriazole,
3-amino-1,2,4 triazole, 1-H-benzotriazole-1-yl-methylisocyanide,
methylene-bis-benzotriazole and naphthotriazole; and The neutral
organic phosphate which forms a component of the formulation may be
present in an amount of 0.01 to 4%, preferably 1.5 to 2.5% by
weight of the composition. The above amine phosphates and any of
the aforementioned benzo- or tolyltriazoles can be mixed together
to form a single component capable of delivering antiwear
performance. The neutral organic phosphate is also a conventional
ingredient of lubricating compositions and any such neutral organic
phosphate falling within the formula as previously defined may be
employed.
[0166] Phosphates for use in the present invention include
phosphates, acid phosphates, phosphites and acid phosphites. The
phosphates include triaryl phosphates, trialkyl phosphates,
trialkylaryl phosphates, triarylalkyl phosphates and trialkenyl
phosphates. As specific examples of these, referred to are
triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate,
ethyldiphenyl phosphate, tributyl phosphate, ethyldibutyl
phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate,
ethylphenyldiphenyl phosphate, diethylphenylphenyl phosphate,
propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate,
triethylphenyl phosphate, tripropylphenyl phosphate,
butylphenyldiphenyl phosphate, dibutylphenylphenyl phosphate,
tributylphenyl phosphate, trihexyl phosphate, tri(2-ethylhexyl)
phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl
phosphate, tripalmityl phosphate, tristearyl phosphate, and
trioleyl phosphate. The acid phosphates include, for example,
2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid
phosphate, oleyl acid phosphate, tetracosyl acid phosphate,
isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid
phosphate, stearyl acid phosphate, and isostearyl acid
phosphate.
[0167] The phosphites include, for example, triethyl phosphite,
tributyl phosphite, triphenyl phosphite, tricresyl phosphite,
tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl
phosphite, trilauryl phosphite, triisooctyl phosphite,
diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl
phosphite.
[0168] The acid phosphites include, for example, dibutyl
hydrogenphosphite, dilauryl hydrogenphosphite, dioleyl
hydrogenphosphite, distearyl hydrogenphosphite, and diphenyl
hydrogenphosphite.
[0169] Amines that form amine salts with such phosphates include,
for example, mono-substituted amines, di-substituted amines and
tri-substituted amines. Examples of the mono-substituted amines
include butylamine, pentylamine, hexylamine, cyclohexylamine,
octylamine, laurylamine, stearylamine, oleylamine and benzylamine;
and those of the di-substituted amines include dibutylamine,
dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine,
dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl
monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine,
benzyl monoethanolamine, phenyl monoethanolamine, and tolyl
monopropanolamine. Examples of tri-substituted amines include
tributylamine, tripentylamine, trihexylamine, tricyclohexylamine,
trioctylamine, trilaurylamine, tristearylamine, trioleylamine,
tribenzylamine, dioleyl monoethanolamine, dilauryl
monopropanolamine, dioctyl monoethanolamine, dihexyl
monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine,
stearyl dipropanolamine, lauryl diethanolamine, octyl
dipropanolamine, butyl diethanolamine, benzyl diethanolamine,
phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine,
triethanolamine, and tripropanolamine. Phosphates or their amine
salts are added to the base oil in an amount of from 0.03 to 5% by
weight, preferably from 0.1 to 4% by weight, relative to the total
weight of the composition.
[0170] Carboxylic acids to be reacted with amines include, for
example, aliphatic carboxylic acids, dicarboxylic acids (dibasic
acids), and aromatic carboxylic acids. The aliphatic carboxylic
acids have from 8 to 30 carbon atoms, and may be saturated or
unsaturated, and linear or branched. Specific examples of the
aliphatic carboxylic acids include pelargonic acid, lauric acid,
tridecanoic acid, myristic acid, palmitic acid, stearic acid,
isostearic acid, eicosanoic acid, behenic acid, triacontanoic acid,
caproleic acid, undecylenic acid, oleic acid, linolenic acid,
erucic acid, and linoleic acid. Specific examples of the
dicarboxylic acids include octadecylsuccinic acid,
octadecenylsuccinic acid, adipic acid, azelaic acid, and sebacic
acid. One example of the aromatic carboxylic acids is salicylic
acid. The amines to be reacted with carboxylic acids include, for
example, polyalkylene-polyamines such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, hexaethyleneheptamine,
heptaethyleneoctamine, dipropylenetriamine,
tetrapropylenepentamine, and hexabutyleneheptamine; and
alkanolamines such as monoethanolamine and diethanolamine. Of
these, preferred are a combination of isostearic acid and
tetraethylenepentamine, and a combination of oleic acid and
diethanolamine. The reaction products of carboxylic acids and
amines are added to the base oil in an amount of from 0.01 to 5% by
weight, preferably from 0.03 to 3% by weight, relative to the total
weight of the composition.
[0171] Important components are phosphites, thiophosphites
phosphates, and thiophosphates, including mixed materials having,
for instance, one or two sulfur atoms, i.e., monothio- or dithio
compounds. As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
[0172] Hydrocarbon substituents, that is, aliphatic (e.g., alkyl or
alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents,
and aromatic-, aliphatic-, and alicyclic-substituted aromatic
substituents, as well as cyclic substituents wherein the ring is
completed through another portion of the molecule (e.g., two
substituents together form an alicyclic radical); the substituted
hydrocarbon substituents, that is, substituents containing
non-hydrocarbon groups which, in the context of this invention, do
not alter the predominantly hydrocarbon substituent (e.g., halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy); and hetero-atom
containing substituents, that is, substituents which, while having
a predominantly hydrocarbon character, in the context of this
invention, contain other than carbon in a ring or chain otherwise
composed of carbon atoms. Heteroatoms include sulfur, oxygen,
nitrogen, and encompass substituents as pyridyl, furyl, thienyl and
imidazolyl. In general, no more than two, preferably no more than
one, non-hydrocarbon substituent will be present for every ten
carbon atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
[0173] The term "hydrocarbyl group," in the context of the present
invention, is also intended to encompass cyclic hydrocarbyl or
hydrocarbylene groups, where two or more of the alkyl groups in the
above structures together form a cyclic structure. The hydrocarbyl
or hydrocarbylene groups of the present invention generally are
alkyl or cycloalkyl groups which contain at least 3 carbon atoms.
Preferably or optimally containing sulfur, nitrogen, or oxygen,
they will contain 4 to 24, and alternatively 5 to 18 carbon atoms.
In another embodiment they contain about 6, or exactly 6 carbon
atoms. The hydrocarbyl groups can be tertiary or preferably primary
or secondary groups; in one embodiment the component is a
di(hydrocarbyl)hydrogen phosphite and each of the hydrocarbyl
groups is a primary alkyl group; in another embodiment the
component is a di(hydrocarbyl)hydrogen phosphite and each of the
hydrocarbyl groups is a secondary alkyl group. In yet another
embodiment the component is a hydrocarbylenehydrogen phosphite.
[0174] Examples of straight chain hydrocarbyl groups include
methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl,
n-dodecyl, n-tetradecyl, stearyl, n-hexadecyl, n-octadecyl, oleyl,
and cetyl. Examples of branched-chain hydrocarbon groups include
isopropyl, isobutyl, secondary butyl, tertiary butyl, neopentyl,
2-ethylhexyl, and 2,6-dimethylheptyl. Examples of cyclic groups
include cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl,
methylcyclohexyl, cycloheptyl, and cyclooctyl. A few examples of
aromatic hydrocarbyl groups and mixed aromatic-aliphatic
hydrocarbyl groups include phenyl, methylphenyl, tolyl, and
naphthyl.
[0175] The R groups can also comprise a mixture of hydrocarbyl
groups derived from commercial alcohols. Examples of some
monohydric alcohols and alcohol mixtures include the commercially
available "Alfol.TM." alcohols marketed by Continental Oil
Corporation. Alfol.TM. 810, for instance, is a mixture containing
alcohols consisting essentially of straight chain, primary alcohols
having from 8 to 12 carbon atoms. Alfol.TM. 12 is a mixture of
mostly C12 fatty alcohols; Alfol.TM. 22+ comprises C 18-28 primary
alcohols having mostly C 22 alcohols, and so on. Various mixtures
of monohydric fatty alcohols derived from naturally occurring
triglycerides and ranging in chain length from C 8 to C 18 are
available from Procter & Gamble Company. "Neodol.TM." alcohols
are available from Shell Chemical Co., where, for instance,
Neodol.TM. 25 is a mixture of C 12 to C 15 alcohols.
[0176] Specific examples of some of the phosphites and
thiophosphites within the scope of the invention include
phosphorous acid, mono-, di-, or tri-thiophosphorous acid, mono-,
di-, or tri-propyl phosphite or mono-, di-, or tri-thiophosphite;
mono-, di-, or tri-butyl phosphite or mono-, di-, or
tri-thiophosphite; mono-, di-, or tri-amyl phosphite or mono-, di-,
or tri-thiophosphite; mono-, di-, or tri-hexyl phosphite or mono-,
di-, or tri-thiophosphite; mono-, di-, or tri-phenyl phosphite or
mono-, di-, or tri-thiophosphite; mono-, di-, or tri-tolyl
phosphite or mono-, di-, or tri-thiophosphite; mono-, di-, or
tri-cresyl phosphite or mono-, di-, or tri-thiophosphite; dibutyl
phenyl phosphite or mono-, di-, or tri-phosphite, amyl dicresyl
phosphite or mono-, di-, or tri-thiophosphite, and any of the above
with substituted groups, such as chlorophenyl or chlorobutyl.
[0177] Specific examples of the phosphates and thiophosphates
within the scope of the invention include phosphoric acid, mono-,
di-, or tri-thiophosphoric acid, mono-, di-, or tri-propyl
phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or
tri-butyl phosphate or mono-, di-, or tri-thiophosphate; mono-,
di-, or tri-amyl phosphate or mono-, di-, or tri-thiophosphate;
mono-, di-, or tri-hexyl phosphate or mono-, di-, or
tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-,
di-, or tri-thiophosphate; mono-, di-, or tritolyl phosphate or
mono-, di-, or trithiophosphate; mono-, di-, or tri-cresyl
phosphate or mono-, di-, or tri-thiophosphate; dibutyl phenyl
phosphate or mono-, di-, or tri-phosphate, amyl dicresyl phosphate
or mono-, di-, or tri-thiophosphate, and any of the above with
substituted groups, such as chlorophenyl or chlorobutyl.
[0178] The phosphorus compounds of the present invention are
prepared by well known reactions. One route the reaction of an
alcohol or a phenol with phosphorus trichloride or by a
transesterification reaction. Alcohols and phenols can be reacted
with phosphorus pentoxide to provide a mixture of an alkyl or aryl
phosphoric acid and a dialkyl or diaryl phosphoric acid. Alkyl
phosphates can also be prepared by the oxidation of the
corresponding phosphites. Thiophosphates can be prepared by the
reaction of phosphites with elemental sulfur. In any case, the
reaction can be conducted with moderate heating. Moreover, various
phosphorus esters can be prepared by reaction using other
phosphorus esters as starting materials. Thus, medium chain (C9 to
C22) phosphorus esters have been prepared by reaction of
dimethylphosphite with a mixture of medium-chain alcohols by means
of a thermal transesterification or an acid- or base-catalyzed
transesterification; see for example U.S. Pat. No. 4,652,416. Most
such materials are also commercially available; for instance,
triphenyl phosphite is available from Albright and Wilson as
Duraphos TPP.TM.; di-n-butyl hydrogen phosphite from Albright and
Wilson as Duraphos DBHP.TM.; and triphenylthiophosphate from Ciba
Specialty Chemicals as Irgalube TPPT.TM..
[0179] The other major component of the present composition is a
hydrocarbon having ethylenic unsaturation. This would normally be
described as an olefin or a diene, triene, polyene, and so on,
depending on the number of ethylenic unsaturations present.
Preferably the olefin is mono unsaturated, that is, containing only
a single ethylenic double bond per molecule. The olefin can be a
cyclic or a linear olefin. If a linear olefin, it can be an
internal olefin or an alpha-olefin. The olefin can also contain
aromatic unsaturation, i.e., one or more aromatic rings, provided
that it also contains ethylenic (non-aromatic) unsaturation.
[0180] The olefin normally will contain 6 to 30 carbon atoms.
Olefins having significantly fewer than 6 carbon atoms tend to be
volatile liquids or gases which are not normally suitable for
formulation into a composition suitable as an antiwear lubricant.
Preferably the olefin will contain 6 to 18 or 6 to 12 carbon atoms,
and alternatively 6 or 8 carbon atoms.
[0181] Among suitable olefins are alkyl-substituted cyclopentenes,
hexenes, cyclohexene, alkyl-substituted cyclohexenes, heptenes,
cycloheptenes, alkyl-substituted cycloheptenes, octenes including
diisobutylene, cyclooctenes, alkyl-substituted cyclooctenes,
nonenes, decenes, undecenes, dodecenes including propylene
tetramer, tridecenes, tetradecenes, pentadecenes, hexadecenes,
heptadecenes, octadecenes, cyclooctadiene, norbornene,
dicyclopentadiene, squalene, diphenylacetylene, and styrene. Highly
preferred olefins are cyclohexene and 1-octene.
[0182] Examples of esters of the dialkylphosphorodithioic acids
include esters obtained by reaction of the dialkyl
phosphorodithioic acid with an alpha, beta-unsaturated carboxylic
acid (e.g., methyl acrylate) and, optionally an alkylene oxide such
as propylene oxide.
[0183] Generally, the compositions of the present invention will
contain varying amounts of one or more of the above-identified
metal dithiophosphates such as from about 0.01 to about 2% by
weight, and more generally from about 0.01 to about 1% by weight,
based on the weight of the total composition.
[0184] The hydrocarbyl in the dithiophosphate may be alkyl,
cycloalkyl, aralkyl or alkaryl groups, or a substantially
hydrocarbon group of similar structure. Illustrative alkyl groups
include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl
groups, n-hexyl, methylisobutyl, heptyl, 2-ethylhexyl, diisobutyl,
isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
Illustrative lower alkylphenyl groups include butylphenyl,
amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewise are
useful and these include chiefly cyclohexyl and the lower
alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may
also be used, e.g., chloropentyl, dichlorophenyl, and
dichlorodecyl.
[0185] The phosphorodithioic acids from which the metal salts
useful in this invention are prepared are well known. Examples of
dihydrocarbylphosphorodithioic acids and metal salts, and processes
for preparing such acids and salts are found in, for example U.S.
Pat. Nos. 4,263,150; 4,289,635; 4,308,154; and 4,417,990. These
patents are hereby incorporated by reference.
[0186] The phosphorodithioic acids are prepared by the reaction of
a phosphorus sulfide with an alcohol or phenol or mixtures of
alcohols. A typical reaction involves four moles of the alcohol or
phenol and one mole of phosphorus pentasulfide, and may be carried
out within the temperature range from about 50C. to about 200C.
Thus, the preparation of O,O-di-n-hexyl phosphorodithioic acid
involves the reaction of a mole of phosphorus pentasulfide with
four moles of n-hexyl alcohol at about 100C for about two hours.
Hydrogen sulfide is liberated and the residue is the desired acid.
The preparation of the metal salts of these acids may be effected
by reaction with metal compounds as well known in the art.
[0187] The metal salts of dihydrocarbyldithiophosphates which are
useful in this invention include those salts containing Group I
metals, Group II metals, aluminum, lead, tin, molybdenum,
manganese, cobalt, and nickel. The Group II metals, aluminum, tin,
iron, cobalt, lead, molybdenum, manganese, nickel and copper are
among the preferred metals. Zinc and copper are especially useful
metals. Examples of metal compounds which may be reacted with the
acid include lithium oxide, lithium hydroxide, sodium hydroxide,
sodium carbonate, potassium hydroxide, potassium carbonate, silver
oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc
hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide,
barium oxide, aluminum oxide, iron carbonate, copper hydroxide,
lead hydroxide, tin butylate, cobalt hydroxide, nickel hydroxide,
nickel carbonate, and the like.
[0188] In some instances, the incorporation of certain ingredients
such as small amounts of the metal acetate or acetic acid in
conjunction with the metal reactant will facilitate the reaction
and result in an improved product. For example, the use of up to
about 5% of zinc acetate in combination with the required amount of
zinc oxide facilitates the formation of a zinc phosphorodithioate
with potentially improved performance properties.
[0189] Especially useful metal phosphorodithloates can be prepared
from phosphorodithloic acids which in turn are prepared by the
reaction of phosphorus pentasulfide with mixtures of alcohols. In
addition, the use of such mixtures enables the utilization of less
expensive alcohols which individually may not yield oil-soluble
phosphorodithioic acids. Thus a mixture of isopropyl and
hexylalcohols can be used to produce a very effective, oil-soluble
metal phosphorodithioate. For the same reason mixtures of
phosphorodithioic acids can be reacted with the metal compounds to
form less expensive, oil-soluble salts.
[0190] The mixtures of alcohols may be mixtures of different
primary alcohols, mixtures of different secondary alcohols or
mixtures of primary and secondary alcohols. Examples of useful
mixtures include: n-butanol and n-octanol; n-pentanol and
2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl
alcohol; isopropanol and 2-methyl-4-pentanol; isopropanol and
sec-butyl alcohol; isopropanol and isooctyl alcohol; and the
like.
[0191] Organic triesters of phosphorus acids are also employed in
lubricants. Typical esters include triarylphosphates, trialkyl
phosphates, neutral alkylaryl phosphates, alkoxyalkyl phosphates,
triaryl phosphite, trialkylphosphite, neutral alkyl aryl
phosphites, neutral phosphonate esters and neutral phosphine oxide
esters. In one embodiment, the long chain dialkyl phosphonate
esters are used. More preferentially, the dimethyl-, diethyl-, and
dipropyl-oleyl phosphonates can be used. Neutral acids of
phosphorus acids are the triesters rather than an acid (HO--P) or a
salt of an acid.
[0192] Any C4 to C8 alkyl or higher phosphate ester may be employed
in the invention. For example, tributyl phosphate (TBP) and tri
isooctal phosphate (TOF) can be used. The specific triphosphate
ester or combination of esters can easily be selected by one
skilled in the art to adjust the density, viscosity etc. of the
formulated fluid. Mixed esters, such as dibutyl octyl phosphate or
the like may be employed rather than a mixture of two or more
trialkyl phosphates.
[0193] A trialkyl phosphate is often useful to adjust the specific
gravity of the formulation, but it is desirable that the specific
trialkyl phosphate be a liquid at low temperatures. Consequently, a
mixed ester containing at least one partially alkylated with a C3
to C4 alkyl group is very desirable, for example, 4-isopropylphenyl
diphenyl phosphate or 3-butylphenyl diphenyl phosphate. Even more
desirable is a triaryl phosphate produced by partially alkylating
phenol with butylene or propylene to form a mixed phenol which is
then reacted with phosphorus oxychloride as taught in U.S. Pat. No.
3,576,923.
[0194] Any mixed triaryl phosphate (TAP) esters may be used as
cresyl diphenyl phosphate, tricresyl phosphate, mixed xylyl cresyl
phosphates, lower alkylphenyl/phenyl phosphates, such as mixed
isopropylphenyl/phenyl phosphates, t-butylphenyl phenyl phosphates.
These esters are used extensively as plasticizers, functional
fluids, gasoline additives, flame-retardant additives and the
like.
[0195] An Extreme pressure agent, sulfur-based extreme pressure
agents, such as sulfides, sulfoxides, sulfones, thiophosphinates,
thiocarbonates, sulfurized fats and oils, sulfurized olefins and
the like; phosphorus-based extreme pressure agents, such as
phosphoric acid esters (e.g., tricresyl phosphate (TCP) and the
like), phosphorous acid esters, phosphoric acid ester amine salts,
phosphorous acid ester amine salts, and the like; halogen-based
extreme pressure agents, such as chlorinated hydrocarbons and the
like; organometallic extreme pressure agents, such as
thiophosphoric acid salts (e.g., zinc dithiophosphate (ZnDTP) and
the like) and thiocarbamic acid salts; and the like can be used. As
the anti-wear agent, organomolybdenum compounds such as molybdenum
dithiophosphate (MoDTP), molybdenum dithiocarbamate (MODTC) and the
like; organoboric compounds such as alkylmercaptyl borate and the
like; solid lubricant anti-wear agents such as graphite, molybdenum
disulfide, antimony sulfide, boron compounds,
polytetrafluoroethylene and the like; and the like can be used.
[0196] The phosphoric acid ester, thiophosphoric acid ester, and
amine salt thereof functions to enhance the lubricating
performances, and can be selected from known compounds
conventionally employed as extreme pressure agents. Generally
employed are phosphoric acid esters, a thiophosphoric acid ester,
or an amine salt thereof which has an alkyl group, an alkenyl
group, an alkylaryl group, or an aralkyl group, any of which
contains approximately 3 to 30 carbon atoms.
[0197] Examples of the phosphoric acid esters include aliphatic
phosphoric acid esters such as triisopropyl phosphate, tributyl
phosphate, ethyl dibutyl phosphate, trihexyl phosphate,
tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl
phosphate, and trioleyl phosphate; and aromatic phosphoric acid
esters such as benzyl phenyl phosphate, allyl diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate,
cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl
diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl
diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl
phosphate, tripropylphenyl phosphate, butylphenyl diphenyl
phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl
phosphate. Preferably, the phosphoric acid ester is a
trialkylphenyl phosphate.
[0198] Examples of the thiophosphoric acid esters include aliphatic
thiophosphoric acid esters such as triisopropyl thiophosphate,
tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl
thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl
thiophosphate, tristearyl thiophosphate, and trioleyl
thiophosphate; and aromatic thiophosphoric acid esters such as
benzyl phenyl thiophosphate, allyl diphenyl thiophosphate,
triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl
thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl
thiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl
phenyl thiophosphate, propylphenyl diphenyl thiophosphate,
dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate,
tripropylphenyl thiophosphate, butylphenyl diphenyl thiophosphate,
dibutylphenyl phenyl thiophosphate, and tributylphenyl
thiophosphate. Preferably, the thiophosphoric acid ester is a
trialkylphenyl thiophosphate.
[0199] Also employable are amine salts of the above-mentioned
phosphates and thiophosphates. Amine salts of acidic alkyl or aryl
esters of the phosphoric acid and thiophosphoric acid are also
employable. Preferably, the amine salt is an amine salt of
trialkylphenyl phosphate or an amine salt of alkyl phosphate.
[0200] One or any combination of the compounds selected from the
group consisting of a phosphoric acid ester, a thiophosphoric acid
ester, and an amine salt thereof may be used.
[0201] The phosphorus acid ester and/or its amine salt function to
enhance the lubricating performances, and can be selected from
known compounds conventionally employed as extreme pressure agents.
Generally employed are a phosphorus acid ester or an amine salt
thereof which has an alkyl group, an alkenyl group, an alkylaryl
group, or an aralkyl group, any of which contains approximately 3
to 30 carbon atoms.
[0202] Examples of the phosphorus acid esters include aliphatic
phosphorus acid esters such as triisopropyl phosphite, tributyl
phosphite, ethyl dibutyl phosphite, trihexyl phosphite,
tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl
phosphite, and trioleyl phosphite; and aromatic phosphorus acid
esters such as benzyl phenyl phosphite, allyl diphenylphosphite,
triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite,
tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl
phosphite, dicresyl phenyl phosphite, ethylphenyl diphenyl
phosphite, diethylphenyl phenyl phosphite, propylphenyl diphenyl
phosphite, dipropylphenyl phenyl phosphite, triethylphenyl
phosphite, tripropylphenyl phosphite, butylphenyl diphenyl
phosphite, dibutylphenyl phenyl phosphite, and tributylphenyl
phosphite. Also favorably employed are dilauryl phosphite, dioleyl
phosphite, dialkyl phosphites, and diphenyl phosphite. Preferably,
the phosphorus acid ester is a dialkyl phosphite or a trialkyl
phosphite.
[0203] The phosphate salt may be derived from a polyamine. The
polyamines include alkoxylated diamines, fatty polyamine diamines,
alkylenepolyamines, hydroxy containing polyamines, condensed
polyamines arylpolyamines, and heterocyclic polyamines.
Commercially available examples of alkoxylated diamines include
those amine where y in the above formula is one. Examples of these
amines include Ethoduomeen T/13 and T/20 which are ethylene oxide
condensation products of N-tallowtrimethylenediamine containing 3
and 10 moles of ethylene oxide per mole of diamine,
respectively.
[0204] In another embodiment, the polyamine is a fatty diamine. The
fatty diamines include mono- or dialkyl, symmetrical or
asymmetrical ethylene diamines, propane diamines (1,2, or 1,3), and
polyamine analogs of the above. Suitable commercial fatty
polyamines are Duomeen C. (N-coco-1,3-diaminopropane), Duomeen
S(N-soya-1,3-diaminopropane), Duomeen T
(N-tallow-1,3-diaminopropane), and Duomeen 0
(N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available
from Armak Chemical Co., Chicago, Ill.
[0205] Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amines such as piperazines and N-amino
alkyl-substituted piperazines are also included. Specific examples
of such polyamines are ethylenediamine, triethylenetetramine,
tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine, tetraethylenepentamine,
hexaethyleneheptamine, pentaethylenehexamine, etc. Higher homologs
obtained by condensing two or more of the above-noted
alkyleneamines are similarly useful as are mixtures of two or more
of the aforedescribed polyamines.
[0206] In one embodiment the polyamine is an ethylenepolyamine.
Such polyamines are described in detail under the heading Ethylene
Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2d
Edition, Vol. 7, pages 22-37, Interscience Publishers, New York
(1965). Ethylenepolyamines are often a complex mixture of
polyalkylenepolyamines including cyclic condensation products.
[0207] Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mixtures to leave,
as residue, what is often termed "polyamine bottoms". In general,
alkylenepolyamine bottoms can be characterized as having less than
2%, usually less than 1% (by weight) material boiling below about
200C. A typical sample of such ethylene polyamine bottoms obtained
from the Dow Chemical Company of Freeport, Tex. designated "E-100".
These alkylenepolyamine bottoms include cyclic condensation
products such as piperazine and higher analogs of
diethylenetriamine, triethylenetetramine and the like. These
alkylenepolyamine bottoms can be reacted solely with the acylating
agent or they can be used with other amines, polyamines, or
mixtures thereof. Another useful polyamine is a condensation
reaction between at least one hydroxy compound with at least one
polyamine reactant containing at least one primary or secondary
amino group. The hydroxy compounds are preferably polyhydric
alcohols and amines. The polyhydric alcohols are described below.
(See carboxylic ester dispersants.) In one embodiment, the hydroxy
compounds are polyhydric amines. Polyhydric amines include any of
the above-described monoamines reacted with an alkylene oxide
(e.g., ethylene oxide, propylene oxide, butylene oxide, etc.)
having from two to about 20 carbon atoms, or from two to about
four. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1,3-propanediol,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and
N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, preferably
tris(hydroxymethyl)aminomethane (THAM).
[0208] Polyamines which react with the polyhydric alcohol or amine
to form the condensation products or condensed amines, are
described above. Preferred polyamines include triethylenetetramine
(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), and mixtures of polyamines such as the above-described
"amine bottoms".
[0209] Examples of extreme pressure additives include sulphur-based
extreme pressure additives such as dialkyl sulphides, dibenzyl
sulphide, dialkyl polysulphides, dibenzyl disulphide, alkyl
mercaptans, dibenzothiophene and 2,2'-dithiobis(benzothiazole);
phosphorus-based extreme pressure additives such as trialkyl
phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl
phosphites, triaryl phosphites and dialkylhydrozine phosphites, and
phosphorus- and sulphur-based extreme pressure additives such as
zinc dialkyldithiophosphates, dialkylthiophosphoric acid, trialkyl
thiophosphate esters, acidic thiophosphate esters and trialkyl
trithiophosphates. These extreme pressure additives can be used
individually or in the form of mixtures, conveniently in an amount
within the range from 0.1 to 2 parts by weight, per 100 parts by
weight of the base oil.
[0210] All the above can be performance enhanced using a variety of
cobase stocks, AN, AB, ADPO, ADPS, ADPM, and/or a variety of
mono-basic, di-basic, and tribasic esters in conjunction with low
sulfur, low aromatic, low iodine number, low bromine number, high
analine point, isoparafin.
EXAMPLES
[0211] We formulated three inventive gear oil blends for comparison
against two commercially available gear oils. All the inventive
blends contained two base stocks and contained the same standard
gear oil additive package.
[0212] The first blend comprises a metallocene catalyzed PAO base
stock with a viscosity of 620 cSt, Kv100.degree. C. The second base
stock contained a PAO with a viscosity of 4 cSt, Kv1.degree. C. The
blend also includes alkylated napthalene, phalate ester and adipate
ester along with a gear oil additive pack.
[0213] The second blend comprises a metallocene catalyzed PAO base
stock with a viscosity of 620 cSt, Kv100.degree. C. The second PAO
base stock with a viscosity of 4 cSt, Kv100.degree. C. The blend
also includes adipate ester along with a gear oil additive
pack.
[0214] The third blend comprises a regular high viscosity PAO with
a viscosity of 100 cSt, Kv100.degree. C. and a low viscosity PAO
with a viscosity of 6 cSt, Kv100.degree. C. The blend also includes
alkylated napthalene, phalate ester and adipate ester along with a
gear oil additive pack.
[0215] Table 4 shows the formulations of the three novel blends
relative to the two commercial synthetic products which serve as
the benchmarks of performance as shown in table 4 the benefit is
most pronounced in the when compared to synethic gear oil A which
is a traditional PAO gear oil with some alkylated naphtaleline. The
three novel formulations provide comparable MSWG efficiency and
operating temperature performance to Polyalkylene glycols ("PAGs")
oils but retain the benefits of PAO oils.
[0216] PAGs have some excellent properties but also have some
inherent poor properties. The excellent properties of PAGS include
viscosity index, foam and air control, efficiency and oxidative
stability. The poor properties include water tolerance, rust
control and compatibility. The novel formulations in Table 4
provide all around excellent properties including comparable
performance to PAGs for excellent viscosity index, foam and air
control, efficiency and oxidative stability while also providing
good water tolerance, compatibility and rust control.
TABLE-US-00004 TABLE 4 ISO VG 460 EXPERIMENTAL COMMERCIAL
Kv100.degree. C. = A B C D E Conventional PAG-based 50-60 cSt
PAO-based lubricant mPAO 620 cSt 45.7 51.7 19.7 lubricant mPAO 450
cSt 54.7 mPAO 300 cSt 60.7 40 cSt PAO 70 4 cSt PAO 41 38 35 29
Cobase stock and 13.3 10.3 10.3 13.3 13.3 Additive package Worm
Gear Ave 152 157 159 169 168 175 150 Sump Temp .degree. F. Worm
Gear Av. 81.1 79.9 79.3 77.6 77.8 76.7 80.5 Efficiency ASTM D3427
75.degree. C. 5.2 5.7 5.9 5.4 7.1 22.4 21 Time to 0.2% Air (min)
ASTM D97 Pour -42 -42 -39 -48 -39 -42 -33 Point .degree. C.
[0217] The data from table 4 is shown in FIG. 3. FIG. 3 is a graph
illustrating the improved air release benefits profile of A, B, C,
D, and E of high viscosity metallocene catalyzed base stocks in
bi-modal blend as compared to the profile of a high viscosity PAO
base stock in a blend with a low viscosity base stock. And a PAG
based lubricant.
[0218] While the examples have been to gear oils, these examples
are not intended to be limiting. The novel formulations provides
improved properties of all lubricating uses including but not
limited to industrial, engine and hydraulic oils.
[0219] The operating temperatures data from table 4 is shown in
FIG. 4. FIG. 4 shows the of the three experimental extreme-modal
formulations A, B, C, D, and E relative to the current commercially
available synthetic PAO and PAG gear oils. Indeed, the thermal
performance of these experimental formulations rival that of the
commercially available PAGs.
[0220] The metallocene based bases stocks in a bi-modal formula
further provide favorable air release benefits. FIG. 5 illustrates
the improved air release of the novel formulations in Table 4 when
compare to commercially available gear oils including typical PAO
and PAG blends.
[0221] In addition, the metallocene based bases stocks in a
bi-modal formula provides favorable low temperature benefits
including favorable pour points compared to PAGs. Favorable pour
points permit better oil pumpability and better equipment startup
at low temperatures. For pour point testing, ASTM D97 is most often
utilized. In this method, oil is slowly cooled at a specific rate,
and examined at 3.degree. C. intervals for flow characteristics.
The lowest temperature where movement is observed is the pour
point. FIG. 6 illustrates the improved pour points of the novel
formulations in Table 4 when compared to commercially available PAG
gear oil blends as well as equivalent performance when compared to
typical PAO gear oil blends.
[0222] In addition to the above examples, there are other base
stocks that give favorable performance when combined with high
viscosity metallocene catalyzed base stocks of greater than 300
cSt, Kv100.degree. C. These base stocks include but are not limited
to GTL, Group III., Group II, PIB, Group V base stocks, including
alkylnaphthalenes, alkylbenzenes, polyalkylene glycols and esters
including polyol esters, trimellitic esters, aromatic esters,
dibasic esters and monobasic esters. In all the above cases, some
portion of Group I base stock can be added to achieve suitable
viscosity and to impart solvency/dispersancy and other property
typical to Group I base stocks.
[0223] In addition, based on the disclosure herein other base
stocks of widely disparate viscosities that give a "bi-modal" or
"extreme-modal" blending result can also be envisioned with the
benefit of the disclosure herein to deliver favorable lubricating
properties. These properties include but are not limited to
micropitting, air release, pour point, low temperature viscosity,
pour point, shear stability, and any combination thereof. While the
benefits discussed herein are primarily for the use of gear oil,
the benefits would apply to all lubricants including marine,
automotive, and industrial. The claims are intended to include all
suitable lubricant applications.
[0224] In one embodiment, no VI improvers are needed due to the
high inherent VI of the base stocks. This benefit permits the
ability to avoid VI improvers that may adversely affect shear
stability. In this embodiment, the shear stability of the lubricant
should be less than 15 percent and even more preferably less than
10 percent and in the most preferred embodiment, there will be
essentially no VI improvers.
[0225] In a preferred embodiment, no transition or alkali metals
are used in the finished formulation. This finished formulation
would provide enhanced hydrolytic stability.
[0226] In another embodiment, another benefit of the improved base
stocks properties is the ability to use less additives. In a
preferred embodiment, the base stock combination provides the
ability to use treat rates less than 10 percent and less than 5
percent.
* * * * *
References