U.S. patent application number 13/250281 was filed with the patent office on 2012-03-15 for lubricant composition with improved varnish deposit resistance.
This patent application is currently assigned to EXXONMOBIL RESEARCH AND ENGINEERING COMPANY. Invention is credited to David G. L. Holt, Andrea B. Wardlow.
Application Number | 20120065112 13/250281 |
Document ID | / |
Family ID | 45807286 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120065112 |
Kind Code |
A1 |
Wardlow; Andrea B. ; et
al. |
March 15, 2012 |
LUBRICANT COMPOSITION WITH IMPROVED VARNISH DEPOSIT RESISTANCE
Abstract
In one embodiment, a lubricating oil with favorable deposit
control is disclosed. The lubricating oil comprises, a major amount
of base stock selected from the group consisting of Group II, Group
III, GTL and any combination thereof, a mannich based dispersant
comprising at least 0.1 and less than 2.0 weight percent of the
lubricating oil, a demulsifier comprising
apolyoxypropylene-polyoxyethylene block copolymer in tricresyl
phosphate (TCP) demulsifier and apolyether glycol demulsifier, the
demulsifiers comprising at least 0.002 to less than 2.0 weight
percent of the lubricating oil, wherein the lubricating oil has a
deposit control value less than 60 mg/kg using 504 hour 120.degree.
C. Dry TOST sludge test and an ASTM D-1401 emulsion characteristic
of less than 60 minutes at 54.degree. C.
Inventors: |
Wardlow; Andrea B.; (Cherry
Hill, NJ) ; Holt; David G. L.; (Medford, NJ) |
Assignee: |
EXXONMOBIL RESEARCH AND ENGINEERING
COMPANY
Annandale
NJ
|
Family ID: |
45807286 |
Appl. No.: |
13/250281 |
Filed: |
September 30, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12383811 |
Mar 27, 2009 |
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13250281 |
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61072432 |
Mar 31, 2008 |
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Current U.S.
Class: |
508/579 |
Current CPC
Class: |
C10M 2215/28 20130101;
C10N 2030/45 20200501; C10M 2215/064 20130101; C10M 2223/047
20130101; C10N 2040/135 20200501; C10M 2215/086 20130101; C10M
2207/026 20130101; C10M 2207/283 20130101; C10M 2215/065 20130101;
C10N 2030/42 20200501; C10M 2205/173 20130101; C10M 2217/043
20130101; C10M 2219/066 20130101; C10M 2209/108 20130101; C10N
2040/12 20130101; C10N 2030/04 20130101; C10M 2203/04 20130101;
C10M 2207/2805 20130101; C10M 2203/1006 20130101; C10M 2203/06
20130101; C10N 2060/14 20130101; C10M 2203/1025 20130101; C10M
2223/041 20130101; C10M 2209/104 20130101; C10M 169/04 20130101;
C10M 2219/044 20130101; C10M 2209/105 20130101; C10M 2215/223
20130101; C10N 2030/10 20130101; C10M 2209/104 20130101; C10M
2209/105 20130101; C10M 2209/107 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101; C10M 2217/043 20130101; C10N 2060/14
20130101; C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M
2217/043 20130101; C10N 2060/14 20130101 |
Class at
Publication: |
508/579 |
International
Class: |
C10M 145/34 20060101
C10M145/34 |
Claims
1. A lubricating oil with favorable deposit control and emulsion
properties, comprising: a) a major amount of base stock selected
from the group consisting of Group II, Group III, GTL and any
combination thereof; b) a mannich based dispersant comprising at
least 0.1 and less than 2.0 weight percent of the lubricating oil;
c) a demulsifier comprising a first
polyoxypropylene-polyoxyethylene block copolymer in TCP, and d) a
polyether glycol demulsifier or a second
polyoxypropylene-polyoxyethylene block copolymer demulsifier,
wherein the demulsifiers comprise at least 0.002 to less than 2.0
weight percent of the lubricating oil, and the lubricating oil has
a deposit control value less than 60 mg/kg using 504 hour
120.degree. C. Dry TOST sludge test and an ASTM D-1401. emulsion
characteristic of less than 60 minutes at 54.degree. C.
2. The lubricating oil of claim 1 further comprising at least one
additive selected from the group consisting of an antiwear
additive, metal passivator, demulsifier, pour point depressant,
rust inhibitor, defoamant and any combination thereof.
3. The lubricating oil of claim 1 wherein the lubricating oil is a
gas turbine oil.
4. The lubricating oil of claim 1 wherein the ethylene oxide in the
second polyoxypropylene-polyoxyethylene block copolymer comprises
less than 25 wt % of the demulsifier, the second
polyoxypropylene-polyoxyethylene block copolymer has a molecular
weight less than 5000, and the lubricating oil has an ASTM D-1401
emulsion characteristic of less than 3 ml emulsion volume at 30
minutes time at 54.degree. C.
5. The lubricating oil of claim 1 wherein the lubricating oil has a
ASTM D-4308 electrical conductivity value of greater than 50
pS/m.
6. The lubricating oil of claim 1 wherein the lubricating oil has
less than 5 PPM calcium and less than 5 PPM zinc.
7. The lubricating oil of claim 6 wherein the lubricating oil has a
less than 50 PPM phosphorous.
8. A method for improving the deposit control and emulsion
properties of a lubricating oil, comprising: a) obtaining a
lubricating oil comprising a major amount of base stock selected
from the group consisting of Group II, Group III, GTL and any
combination thereof, and b) adding to the lubricating oil a mannich
based dispersant comprising at least 0.1 and less than 2.0 weight
percent of the lubricating oil, a demulsifier comprising a first
polyoxypropylene-polyoxyethylene block copolymer in TCP, and a
polyether glycol demulsifier or a second
polyoxypropylene-polyoxyethylene block copolymer demulsifier, the
demulsifiers comprising at least 0.002 to less than 2.0 weight
percent of the lubricating oil, wherein the lubricating oil has a
deposit control value less than 60 mg/kg using 504 hour 120.degree.
C. Dry TOST sludge test, and an ASTM D-1401 emulsion characteristic
of less than 60 minutes at 54.degree. C.
9. The method of claim 8, wherein the lubricating oil further
comprises at least one additive selected from the group consisting
of an antiwear additive, metal passivator, demulsifier, pour point
depressant, rust inhibitor, defoamant and any combination
thereof.
10. The method of claim 8 wherein the lubricating oil is a gas
turbine oil.
11. The method of claim 8 wherein the ethylene oxide in the second
polyoxypropylene-polyoxyethylene block copolymer comprises less
than 25 wt % of the demulsifier, the second
polyonfpropylene-polyoxyethylene block copolymer has a molecular
weight less than 5000, and the lubricating oil has an ASTM D-1401.
emulsion characteristic of less than 3 ml emulsion volume at 30
minutes time at 54.degree. C.
12. The method of claim 8 wherein the lubricating oil has an ASTM
D-4308 electrical conductivity value of greater than 50 pS/m.
13. The method of claim 8 Wherein the lubricating oil has a less
than 5 PPM calcium and less than 5 PPM zinc.
14. The method of claim 13 wherein the lubricating oil has a less
than 50 PPM phosphorous.
Description
[0001] This application is a continuation-in-part of U.S. Ser. No.
12/383,811 filed Mar. 27, 2009, which claims the benefit of
provisional application U.S. Ser. No. 61/072,432 filed Mar. 31,
2008.
BACKGROUND
[0002] The art of formulating lubricating oil compositions has
become more complex as a result of increased government and user
environmental standards and increased user performance
requirements. Lubricants are typically marketed based upon features
such as fluid durability, deposit control, antiwear protection,
filterability, water tolerance, rust/corrosion protection, and
viscosity.
[0003] Deposit or varnish is a growing problem in many hydraulic
and sensitive lubrication applications, such as gas turbine
lubrication. Varnish formation is usually the result of a complex
series of events which lead to lubricant degradation. There are two
common causes of oil degradation. One cause is oxidation at
elevated temperatures leading to the formation of decomposition
products, including acids and insoluble particulate, referred to as
deposits, varnish, sludge. The second cause is thermal degradation,
such as, pressure induced dieseling or micro-dieseling which occurs
when entrained air bubbles are collapsed under high pressure.
[0004] Deposit varnish is measured using a 504 hour 120.degree. C.
DRY-TOST sludge test, which is a modified waterless ASTM D943 TOST
test. This DRY-TOST test method was developed by Mitsubishi Heavy
Industries in order to evaluate in short time the sludge or varnish
formation tendency of turbine oils. The Dry-TOST conforms to the
ASTM D943 test with the modified conditions shown in the table
below. After the 504-hr test period, leave the test tube to stand
for 24 hours at room temperature and then measure the deposit
amount. The sludge or varnish amount equals to the amount of filter
residues that 100 g of oil is tittered through a 1 .mu.m Millipore
filter. A sludge amount of less than 100 mg/kg (ppm) is an
acceptable result. The table below lists the items and test
conditions for this test.
TABLE-US-00001 Items Test Condition Test Oil Quantity 360 ml Test
Temperature 120.degree. C. .+-. 0.2.degree. C. Oxygen Gas Flow Rate
3.0 .+-. 0.1 L/h Water Not Added Catalyst Fe and Copper Wire
[0005] It is well known that API Group II and III base stock oils
and GTL are typically better than API Group I base oils, Group II
and II base stocks are better because of the oxidation stability of
hydroproceesed or hydrocracked base stocks as well as enhanced
viscosity and temperature properties compared to conventional
solvent refined base stocks. Consequently, many lubricants are
being formulated with API Group II and III base stock. A known
deficiency of these non-polar, high saturated API Group II and III
base stocks are their lower ability to solubilize or suspend
lubricant degradation by-products in solution once formed. For this
reason, API Group II/III based lubricants are more susceptible to
deposit formation once oil degradation has began.
[0006] A large number of failures in turbine-generator applications
have been associated .sup.-with varnish and sludge formation.
Sludge and Varnish are insoluble materials formed as a result of
either degradation reactions in the oil, contamination of oil or
both. Explanations typically include the nature of the base oil,
additive instability or degradation, bulk oil oxidation,
electrostatic discharge, and low electrical conductivity, among
others.
[0007] Recently, much attention has been directed to the potential
role of fluid electrification and electrostatic discharge as a
prominent contributor to sludge and varnish formation in turbine
systems. Static discharge is a form of localized thermal
degradation. Electrostatic charge generation occurs in fluids
systems as a result of internal molecular friction and electrical
potential between the fluid and machine surfaces.
[0008] The magnitude of the static charge within the oil depends on
many factors and grounding of the machine itself has little impact
toward mitigating i charge propagation. This is because the oil is
nonconductive and effectively self-insulates the charged fluid
zones from grounded surfaces. Once the charges build up in the
working fluid zones, including reservoirs and filter housings, the
subsequent static discharging may cause localized thermal-oxidative
oil degradation.
[0009] There is a need to find a formulation that uses API Group
II, Group and GTL base stocks in a formulation that provides
favorable deposit formulation properties. Accordingly, this
invention satisfies that need.
SUMMARY
[0010] In one embodiment, a lubricating oil with favorable deposit
control is disclosed. The lubricating oil comprises, a major amount
of base stock selected from the group consisting of Group II, Group
III, GTL and any combination thereof, a mannich based dispersant
comprising at least 0.1 and less than 2.0 weight percent of the
lubricating oil, a demulsifier comprising a
polyoxypropylene-polyoxyethylene block copolymer in tricresyl
phosphate (TCP) demulsifier and a polyether glycol demulsifier, the
demulsifiers comprising at least 0,002 to less than 2.0 weight
percent of the lubricating oil, the lubricating oil has a deposit
control value less than 60 mg/kg using the 504 hour 120.degree. C.
DRY LOST sludge test and an ASTM D-1401 emulsion characteristic of
less than 60 minutes at 54.degree. C., Alternatively, the
demulsifier may comprise a second polyoxypropylene-polyoxyethylene
block copolymer demulsifier in place of the polyether glycol
demulsifier.
[0011] In a second embodiment, a method to improve deposit control
is disclosed. This method comprises, obtaining a lubricating oil
comprising a major amount of base stock selected from the group
consisting of Group II, Group III, GTL and any combination thereof,
a mannich based dispersant comprising at least 0.1 and less than
2.0 weight percent of the lubricating oil, a demulsifier comprising
a polyoxypropylene-polyoxyethylene block copolymer in TCP
demulsifier and a polyether glycol demulsifier, the demulsifiers
comprising at least 0.002 to less than 2.0 weight percent of the
lubricating oil, wherein the lubricating oil has a deposit control
value less than 60 mg/kg using 504 hour 120.degree. C. DRY TOST
sludge test and an ASTM D-1401 emulsion characteristic of less than
60 minutes at 54.degree. C., and lubricating with the lubricating
oil. Alternatively, the demulsifier may comprise a second
polyoxypropylene-polyoxyethylene block copolymer demulsifier in
place of the polyether glycol demulsifier.
[0012] In a third embodiment, a method of formulating a lubricating
oil to improve deposit control and emulsion properties is
disclosed. This method comprises obtaining a major amount of base
stock selected from the group consisting of Group II, Group III,
GTL and any combination thereof, a mannich based dispersant
comprising at least 0.1 and less than 2.0 weight percent of the
lubricating oil, a demulsifier comprising a
polyoxypropylene-polyoxyethylene block copolymer in TCP demulsifier
and a polyether glycol demulsifier, the demulsifiers comprising at
least 0.002 to less than 2.0 weight percent of the lubricating oil,
and blending the base stocks, demulsifiers and dispersants to have
a deposit control value less than 60 mg/kg using 504 hour
120.degree. C. DRY TOST sludge test and an ASTM D-1401 emulsion
characteristic of less than 60 minutes at 54.degree. C.
Alternatively, the demulsifier may comprise a second
polyoxypropylene-polyoxyethylene block copolymer demulsifier in
place of the polyether glycol demulsifier.
DETAILED DESCRIPTION
[0013] The present invention will be described in connection with
its preferred embodiments. However, to the extent that the
following description is specific to a particular embodiment or a
particular use of the invention, this is intended to be
illustrative only, and is not to be construed as limiting the scope
of the invention. On the contrary, it is intended to cover all
alternatives, modifications, and equivalents that are included
within the spirit and scope of the invention, as defined by the
appended claims.
[0014] In one embodiment we have discovered a lubricant composition
that comprises either a API Group II or III or GTL base stocks or
combinations thereof with antioxidants and other additives when
formulated with a specific mannich-based dispersant/demulsifier
combination yields an unexpected improvement in deposit control
while maintaining good demulsability. Unexpectedly, not all
dispersants provided this cleanliness benefit in this
application.
[0015] While dispersants are known to improve deposit control, they
are polar in nature and tend to be emulsive and provide poor water
separation. An additional benefit in one embodiment of this
lubricant composition is that the final product also exhibits good
demulsification by ASTM D-1401. This method is a rapid test that
involves mixing together 40 ml of oil and 40 nil of water for 5
minutes at 1500 rpm with an impeller. The mixture is allowed to
stand and the time for the water, oil and any emulsion phase to
separate is recorded. This test is conducted at 54.degree. C.
(130.degree. F.) for viscosity below 90 cSt at 40.degree. C. A
generally acceptable result is 30 minutes maximum time to 3 ink of
emulsion remaining.
[0016] The acceptable treat range for the mannich based dispersants
is at least 0.1 to less than 2.0 weight percent. A preferred treat
range is at least 0.2 to less than 0.5 weight percent and a most
preferred treat range is 0.2 and less than 0.4 weight percent.
[0017] In one embodiment, we have discovered that the demulsifiers
comprise a polyoxypropylene-polyoxyethylene block copolymer in TCP
demulsifier and a polyether glycol demulsifier, the demulsifiers
comprising at least 0.002 to less than 2.0 weight percent of the
lubricating oil. The polyether glycol can be Lubrizol 5957. The
polyoxypropylene-polyoxyethylene block copolymer has an ethylene
oxide content of 10 wt %, an average molecular weight of 2,750
g/mol, and an HLB (Hydrophile-Lipophile Balance) of less than
10.
[0018] In another embodiment, we have discovered that a
polyoxypropylene-polyoxyethylene block copolymer demulsifier is
effective in place of the polyether glycol demulsifier at the same
concentration. In this embodiment, the
polyoxypropylene-polyoxyethylene block copolymer has an ethylene
oxide content of 10 wt %, an average molecular weight of 4400, and
an HLB of less than 10. An ethylene oxide content of 25 wt % and a
molecular weight of 5000 would be the upper limits of acceptability
for a polyoxypropylene-polyoxyethylene block copolymer demulsifier
additive.
[0019] The acceptable treat ranges for the demulsifiers is at least
0.002 to less than 2.0 weight percent. A preferred treat range is
at least 0.01 to less than 0.1 weight percent and a most preferred
treat range is 0.01 and less than 0.05 weight percent.
[0020] The formulation demonstrates excellent varnish deposit
properties using the 504 hour 120.degree. C. DRY TOST sludge test.
Preferably the formulation should be a value less than 60 mg/kg,
more preferably a value less than 50 mg/kg and most preferably a
value less than 25 mg/kg.
[0021] In another embodiment, we have discovered the claimed
invention provides excellent electrical conductivity ("EC"). The
test used was D-4308 at 32.degree. F. A sample of liquid
hydrocarbon is introduced into a clean conductivity cell which is
connected in series to a battery voltage source and a sensitive dc
ammeter. The conductivity, automatically calculated from the
observed peak current reading de voltage and cell constant using
Ohm's law, appears as a digital value in either a manual or
automatic mode of meter operation. Low electrical conductivity can
results in static charge build up when machines are shutdown or
idling. Having higher electrical conductivity can prevent a
phenomena of static discharge which has been implicated as one root
cause of varnish deposit formation in gas turbines equipped with
fine filtration and operating at high flowrate. Preferably the
electrical conductivity should be at least 50 pS/m and more
preferably at least 60 pS/m and most preferably greater than 100
pS/m.
[0022] In another embodiment, the formulation should have low
amounts of calcium and zinc. The preferred embodiment is less than
5 PPM zinc and less than 5 PPM calcium. The more preferred
embodiment is less than 5 PPM zinc and less than 5 PPM calcium and
less than 50 PPM phosphorus. An even more preferred embodiment is
less than 1 PPM zinc, less than 1 PPM calcium and less than 5 PPM
phosphorous.
[0023] A formulator skilled in the art, with the benefit of the
disclosure herein would recognize the benefits of adding additional
additives to the formulation. Preferably, the formulation would
comprise at least one additive selected form the group consisting
of an antiwear additive, metal passivator, demulsifier, pour point
depressant, rust inhibitor, defoamant and any combination thereof.
Additional information regarding base stocks and additives are
provided below. Preferably, calcium containing additive, such as
calcium sulfonates, would not be used due potential reaction to
form calicuim carboxylate soaps with commonly used ashless rust
inhibitors used in typical formulations.
Base Stocks:
[0024] 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 I summarizes
properties of each of these five groups.
TABLE-US-00002 TABLE 1 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
[0025] 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.
[0026] 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.
[0027] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds, and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and 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.
[0028] 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.
[0029] 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.
[0030] 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.
[0031] 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 5 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.
[0032] 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.
[0033] 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.
Additives:
[0034] 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.
[0035] 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 intended to
limit the claims.
[0036] Suitable uses of amides 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.
[0037] 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 is carbon atoms.
[0038] 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.
[0039] 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.
[0040] 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-methyl pyrrole,
2-(2-aminoethyl)-1-methyl pyrrolidine 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.
[0041] 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.
[0042] Aromatic amities 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 is 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-dodecyl aniline,
cyclohexyl-substituted naphthylamine, phenathiazines, and
thienyl-substituted aniline.
[0043] 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.
[0044] 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.
[0045] 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.
[0046] 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.
[0047] 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.
[0048] 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, Texas 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.
[0049] The dispersants are selected from: Mannich bases that are
condensation reaction products of a high molecular weight phenol,
an alkylene polyamine and an aldehyde such as formaldehyde. The
phenol typically has an R group that is about C12 (e.g.,
tetrapropyl) or higher (e.g., polyisobutyl with an Mn of from 800
to 3000 or higher). The alkylene polyamine may be any amine of the
general structure:
H.sub.2N--(CH.sub.2--CH.sub.2--NH).sub.X--CH.sub.2CH.sub.2--NH.sub.2,
where X=0 (ethylenediamine), X=1 (diethylenetriamine), X=2 (TETA),
or X=3 (TEPA) tetraethylenepentamine). Polyamine bottoms where X=7
or more may also be used. In addition to formaldehyde,
acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde,
furfural and 2-ethythexanal may also be used as the aldehyde. The
Mannich based dispersants can be borated or unborated. An example
of a borated Mannich dispersant is Amoco 9250 and a non-borated is
Amoco 9251.
[0050] 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.
[0051] 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 I))
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%.
[0052] 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;
polyalkykliphenylamines such as tetrabutyldiphenylamine,
tetrahexyldiphenylamine, tetraoctyldiphenylamine and
tetranonyldiphenylamine; and naphthylamines such as
.alpha,-naphthylamine, phenyl-.alpha.-naphthylamine,
butylpenyl-.alpha.-naphthylamine,
pentylphenyl-.alpha.-naphthylamine,
hexylphenyl.alpha.-naphthylamine,
heptylphenyl-.alpha.-naphthylamine,
octylphenyl-.alpha,-naphthylamine and
nonylphenyl-.alpha.-naphthytamine. 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.
[0053] Oxidation inhibitors, organic compounds containing 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; with ratios of amine/phenolic to be
from 1:10 to 10:1 of the mixtures preferred.
[0054] 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-hydroxybenzylmercaptooctyl 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-butylphenol) (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-hydroxyphenyl)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-hydroxy-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"),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)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.degree.
-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester,
2-(3',5'-di-t-butyl-4-hydroxyphenyl)-methyl-4-(2'',4''-di-t-butyl-3''-hyd-
roxyphenyl)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.
[0055] Viscosity index improvers and/or pour point depressants
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.
[0056] Other examples of viscosity index improvers 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.
[0057] 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.
[0058] 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%.
[0059] Anti-rust additives include (short-chain) alkenyl succinic
acids, partial esters thereof and nitrogen-containing derivatives
thereof. 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.
[0060] 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 acids.
[0061] 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).
[0062] 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-tridecytamine, dimyristylamine,
di-n-pentadecylamine, dipalmitylamine, di-n-pentadecylamine,
distearylamine, di-n-nonadecylamine, di-n-eicosytamine,
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.
[0063] Examples of the aforementioned N-alkylpolyalkyenediamines
include: ethylenediamines such as taurylethylenediamine, coconut
ethylenediamine, n-tridecylethylenediamine-,
myristylethylenediamine, n-pentadecylethytenediamine,
palmitylethylenediamine, n-heptadecylethytenediamine,
stearylethylenediamine, n-nonadecylethylenediamine,
n-eicosylethytenediamine, n-heneicosylethylenediamine,
n-docosylethylendiamine, n-tricosylethylenediamine,
n-pentacosylethylenediamime, oleylethylenediamine, beef
tallow-ethylenediamine, hydrogenated beef tallow-ethylenediamine
and soy beam-ethylenediamine; propylenediamines such as
laurylpropylenediamine, coconut propylenediamine,
n-tridecylpropylenediamine, myristylpropylenediamine,
n-pentadecylpropylenediamine, palmitylpropylenediamine,
n-heptadecylpropylenediamine, stearylpropylenediamine,
n-nonadecylpropylenediamine, n-eicosylpropylenediamine,
n-heneicosylpropyenediamine, n-docosylpropylendiamine,
n-tricosylpropylenediamine, n-pentacosylpropyenediamine, diethylene
triamine (DETA) or triethylene tetramine (TETA),
oleylpropylenediamine, beef tallow-propylenediamine, hydrogenated
beef tallow-piopylenediamine and soy bean-propylenediamine;
butylenediamines such as laurylbutylenediamine, coconut butyl
enediamine, n-tridecylbutylenediamine-, myristylbutylenediamine,
n-pentadecylbutylenediamine, stearylbutylenediamine,
n-eicosylhutylenediamine, n-heneicosylbutylenediamine,
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,
myristylpentylenediamine, palmitylpentylenediamine,
stearylpentylenediamine, oleyl-pentylenediamine, beef
tallow-pentylenediamine, hydrogenated beef tallow-pentylenediamine
and soy bean pentylenediamine.
[0064] Demulsifying agents: include alkoxylated phenols and
phenol-formaldehyde resins and synthetic alkylaryl sulfonates such
as metallic dinonylnaphthatene sulfonates. A demulsifying 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.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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 100 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.
[0069] Metal deactivating compounds/Corrosion inhibitors: include
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 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. 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 is halogens, nitro,
amino, mercapto, etc. Examples of suitable compounds are
benzotriazole and the tolyltriazoles, ethylbenzotriazoles,
hexylbenzotriazoles, octylbenzotriazoles 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.
[0070] 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.
[0071] 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. Cylcoalkyl is for
example cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl
or cyclododecyl. Aralkyl is for example benzyl, 2-phenylethyl,
benzhydryl or naphthytmethyl.
[0072] Aryl is for example phenyl or naphthyl. The heterocyclic
group is for example a morpholine, pyrrolidine, piperidine or a
perhydroazepine ring. 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.
[0073] 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-dodecytaminomethyl)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'-perhydoroazepinomethyl)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-ethythexyl)-methyl
benzotriazole, N,N-bis-(1- or 4-triazolytmethyl)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-triazolytmethyl)ethylene diamine,
[0074] 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-dioctylauainornethyl-2,3-benzotriazole; benzotriazole derivatives
such as the 1-alkyltolutriazoles, for example,
1-dioctylaminomethyl-2,3-tolutriazole; benzimidazole and
benzimidazole derivatives or concentrates and/or mixtures
thereof.
[0075] Anti-wear agents/Extreme pressure agent/Friction Reducer:
aryl phosphates and phosphites, and metal or ash-free carbamates. 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.
[0076] 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); Alibi 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.
[0077] 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.
[0078] 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.
[0079] 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.
[0080] 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 lauryl
amine. Examples of secondary monoamines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, dicyclopentylamine,
dicyclohexylamine, methylbutylamine, ethylhexylamine, etc.
[0081] An amine is a fatty (C.sub.8-30) amine which includes
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,
n-hexadecylamine, n-octadecytamine, 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 OL, Armeen T, Armeen HT,
Armeen S and Armeen SD, wherein the letter designation relates to
the fatty group, such as coco, oleyl, tallow, or stearyl
groups.
[0082] Other useful amines include primary ether amines, such as
those represented by the formula, R''(OR') x NH 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 is 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.
[0083] 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-octadecytamine, 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 amities (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. Pat. 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-aminoalklthiomorpholines,
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.
[0084] 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,
heptadeceneyl derived oleyl 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 Diets-Alder
reaction products of unsaturated monocarboxylic acids with
unsaturated carboxylic acids (such as acrylic, methacrylic, maleic,
furmaric, 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.
[0085] 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.
[0086] 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 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.
[0087] 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, 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.
[0088] 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-ethythexyl 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.
[0089] The phosphites include, for example, triethyl phosphite, tri
butyl 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.
[0090] The acid phosphites include, for example, dibutyl
hydrogenphosphite, dilauryl hydrogenphosphite, dioleyl
hydrogenphosphite, distearyl hydrogenphosphite, and diphenyl
hydrogenphosphite. Amines that form amine salts with such
phosphates include, for example, mono-substituted amines,
di-substituted amines and tri-substituted amities. Examples of the
mono-substituted amities include butylamine, pentylamine,
hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine,
oleylamine and benzylamine; and those of the di-substituted
airlines 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 amities include tributylamine, tripentylamine,
trihexyl amine, tricyclohexylamine, trioctylamine, trilaurylamine,
tristearylamine, trioleylamine, tribenzylamine, dioleyl
monoethanolamine, dilauryl monopropanolamine, dioctyl
monoethanolamine, dihexyl monopropanolamine, butyl
monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine,
lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine,
benzyl diethanolamine, phenyl diethanolamine, tolyl
dipropanolamine, xylyl diethanolamine, triethanolamine, and
tripropanolamine.
[0091] 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.
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,
cicosanoic acid, behenic acid, triacontanoic acid, caproleic acid,
undecylenic acid, oleic acid, linolenic acid, erucic acid, and
linoteic 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, triethylenetetrarnine,
tetraethylenepentamine, pentaethylenehexamine,
hexaethyleneheptamine, heptaethyteneoctamine, di propylenetriamine,
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.
[0092] Important components are phosphites. 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: 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,
hydroxy, alkoxy, nitro); 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.
[0093] 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 optimaly 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.
[0094] 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.
[0095] 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.
[0096] Specific examples of some of the phosphites within the scope
of the invention include phosphorous acid, mono-, di-, or
tri-propyl phosphite; mono-, di-, or tri-butyl phosphite, di-, or
tri-amyl phosphite; mono-, di-, or tri-hexyl phosphite; mono-, di-,
or tri-phenyl; mono-, di-, or tri-tolyl phosphite; mono-, di-, or
tri-cresyl phosphite; dibutyl phenyl phosphite or mono-, di-, or
tri-phosphite, amyl dicresyl phosphite.
[0097] 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. 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..
[0098] 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.
[0099] 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.
[0100] 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.
[0101] 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-peritanol; isopropanol and
sec-butyl alcohol; isopropanol and isooctyl alcohol; and the
like.
[0102] 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 phohphonates can be used. Neutral acids of
phosphorus acids are the triesters rather than an acid (HO--P) or a
salt of an acid.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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, 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.
[0107] Examples of the phosphoric acid esters include aliphatic
phosphoric acid esters such as triisopropyl phosphate, tributyl
phosphate, ethyl dibutyl phosphate, trihexyl phosphate,
tri-2-ethythexyl 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.
[0108] Also employable are amine salts of the above-mentioned
phosphates. 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.
[0109] One or any combination of the compounds selected from the
group consisting of a phosphoric acid ester, and an amine salt
thereof may be used. 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.
[0110] 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 phenyl 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.
[0111] 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.
[0112] 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 O
(N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available
from Armak Chemical Co., Chicago, Ill.
[0113] Such at alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amities 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.
[0114] 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.
[0115] 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
200 C. 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 amities, 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 amities 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).
[0116] 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".
[0117] 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. An 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
[0118] We have run several tests to show the benefits of the
inventive formulations. As shown in Table 2, seven examples were
run and are labeled Examples A, B, C, D, E, F, and G.
TABLE-US-00003 TABLE 2 Descriptions Type A B C D E F G Group I 150
SUS neutral Base Stock bal 98.27 Group II 4cst at 100 C. Base Stock
10 19.5 19.5 19.29 19.835 Group III 6 cst at 100 C. Base Stock 84.1
79 79 79 70 Group V Base Stock 3 Borated Mannich based Dispersant
0.2 0.4 0.25 0.4 disperant (borated polyisobutylene-phenol +
formaldehyde & tetraethylene pentamine) PIBSA-TEPA Dispersant
0.2 PIBSA (polyisobutylene Dispersant 1.0 siccinic anhydride)
Polyether glycol (Lubrizol Demulsifier 0.01 0.01 0.01 0.01 5957)
Polyoxtpropylene- Demulsifier 0.01 0.01 0.02 0.02 polyoxyethylene
block copolymer (MW2750) in TCP) Metal sulfonate Demulsifier 0.3
Aromatic Amine Antioxidant 0.5 0.6 0.6 0.6 0.4 0.3 Hindered
Phenolic Antioxidant 0.5 0.3 0.3 0.3 0.3 0.3 Metal passivator Metal
passivator 0.01 0.1 0.03 Rust inhibitor Rust inhibitor 0.2 0.2 0.2
0.2 0.2 0.12 Non Si defoamant Defoamant 0.15 0.15 0.15 0.15 0.15 Si
defoamant Defoamant 0.01 0.02 Pour depressant Pour depressant 0.03
0.03 0.03 0.03 0.03 0.1 0.03 Phosphorus antiwear Antiwear 0.6 D2272
- Rotary Pressure minutes 1258 1232 1168 2623 141 965 Vessel Oxid -
Turbine Oil MHI - 504 Hr Dry TOST mg/kg 63 405 23 4 56 5602 47
sludge at 120.degree. C. D1401 - Emulsion Layer volumes, ml 41-39-0
41-39-0 41-39-0 41-38-1 40-39-1 40-39-1 0-0-80 Characteristics @
54.degree. C. (oil-water-emuls) D1401 - Emulsion Time to 3 ml emul,
10 10 20 30 25 15 >60 Characteristics @ 54.degree. C. minutes
D4308 - Electrical pS/m 5 65 114 -- Conductivity at 32.degree. F.
D4308 - Electrical pS/m 12 97 167 Conductivity at 70.degree. F.
D5185 - Calcium ppm <0.5 <0.5 <0.5 <0.5 0.5 64 <2
D5185 - Phosphorus ppm <5 <5 <5 16 20 689 <5 D5185 -
Zinc ppm <0.5 <0.5 0.6 <0.5 0.9 <0.5 <2
[0119] Blends C, D, and E are formulations showing various
inventive embodiments. Blends A, B, F, and G are typical commercial
gas turbine engine oils for comparison. As can be seen in Table 2,
inventive examples C, D, and E have superior properties in the 504
Hour 120.degree. C. Dry TOST sludge test compared to comparative
Examples A, B, and F. Example A has none of the Mannich based
dispersant, the polyether glycol demulsifier or the
polyoxypropylene-polyoxyethylene block copolymer (MW2750) in TCP
demulsifier. Example B has the polyether glycol demulsifier and the
polyoxypropylene-polyoxyethylene block copolymer (MW2750) in TCP
demulsifier, but not the Mannich based dispersant. Example F has
the Mannich based dispersant but not the polyether glycol
demulsifier or the polyoxypropylenepolyoxyethylene block copolymer
(MW2750) in TCP demulsifier. Example G is a typical Group I
commercial gas turbine oil which provides adequate deposit control
but has the drawbacks of Group I base stocks with poor emulsion
characteristics.
[0120] Table 3, Examples H and I, shows similar improvement in the
sludge test when a polyoxypropylene-polyoxyethylene block copolymer
(MW4400) is used in place of the polyether glycol.
TABLE-US-00004 TABLE 3 Example H Example I Chemical names
Components 1 DiPhenylamine type Antioxidant 1 0.3 0.3 Hindered
phenol Antioxidant 2 0.3 0.3 PANA type Antioxidant 3 0.3 0.3 Rust
inhibitor Rust inhibitor 1 0.2 0.2 Dithiocarbamate Metal passivator
1 0.2 0.2 Tolytrizole type Metal passivator 2 0.01 0.01 Ashless
dithiophosphate Antiwear 0.008 0.008 Borated Mannich based
Dispersant 0.35 0.35 dispersant (borated polyisobutylene-phenol +
formaldehyde & tetra-ethylene pentamine) Polyoxypropylene-
Demulsifier 1 0.02 0.02 polyoxyethylene block copolymer (MW2750) in
TCP) Polyether glycol (Lubrizol 5957) Demulsifier 2 0.01
Polyoxypropylene- Demulsifier 3 0.01 polyoxyethylene block
copolymer (MW4400) Non-Si defoamant Defoamant 0.2 0.2 Pour point
depressant PPD 0.01 0.01 Alkylated Naphthalene Gp V 3 3 Group III
Gp III 16.282 16.282 Group III Gp III 79 79 Method/Description
Description Unit MHI - 504 Hr Dry TOST sludge Sludge mgkg 6 5 at
120.degree. C. D2272 - RPVOT on test oil after Oxidation Stability
minutes/% of new 1073/97% 1224/93% 504 Hr Dry TOST test retention
oil value MHI - 1000 Hr Dry TOST sludge Sludge mg/kg 18 40 at
120.degree. C. D2272 - RPVOT on test oil after Oxidation Stability
minutes/% of new 870/79% 1124/85% 1000 Hr Dry TOST test retention
oil value D1401 - Emulsion Characteristics ASTM Time minutes 20, 15
15, 15 @ 54.degree. C. D1401 - Emulsion characterisitics Layer
volumes, ml mL 39-39-2, 40-37-3 40-39-1, 40-37-3 @ 54.degree. C.
(oil-water-emuls) D2272 Rotary Pressure Vessel RPVOT minutes 1101
1315 Oxid - Turbine Oil DIN 51354/FZG Fail Stage 10 10
[0121] Examples C, D, and E all have favorable deposit control and
emulsion characteristics. This demonstrates the importance in this
embodiment, of having either a Group II or Group III base stocks or
combination thereof and having both a mannich based dispersant, a
demulsifier comprised of a polyether glycol and a
polyoxypropylene-polyoxyethylene block copolymer (MW2750) in TCP.
Alternatively, the demulsifier may be comprised of a
polyoxypropylene-polyoxyethylene block copolymer (MW4400) and a
polyoxypropylene-polyoxyethylene block copolymer (MW2750) in
TCP.
[0122] While the examples are mostly to gas turbine engine oil
formulations. Persons skilled in the art would recognize the
applicability to all situations where a good deposit control and
emulsion properties are desired. Other suitable uses include but
are not limited to compressor and hydraulic oils. Applicants intend
to capture all situations in which the claimed lubricant would be
beneficial.
* * * * *
References