U.S. patent application number 14/189565 was filed with the patent office on 2014-09-18 for method for improving emulsion characteristics of engine oils.
This patent application is currently assigned to ExxonMobil Research and Engineering Company. The applicant listed for this patent is Douglas Edward Deckman, Benjamin D. Eirich, Jacob Joseph Habeeb, Abhimanyu Onkar Patil. Invention is credited to Douglas Edward Deckman, Benjamin D. Eirich, Jacob Joseph Habeeb, Abhimanyu Onkar Patil.
Application Number | 20140274837 14/189565 |
Document ID | / |
Family ID | 50382553 |
Filed Date | 2014-09-18 |
United States Patent
Application |
20140274837 |
Kind Code |
A1 |
Eirich; Benjamin D. ; et
al. |
September 18, 2014 |
METHOD FOR IMPROVING EMULSION CHARACTERISTICS OF ENGINE OILS
Abstract
A method for improving the ability of an engine lubricating oil
contaminated with water and fuel to emulsify water contamination by
using as the engine lubricating oil a formulated oil including a
lubricating oil base stock as a major component and a coupled block
copolymer as a minor component. A method for improving
thermo-oxidative stability and elastomer compatibility in an engine
lubricated with a lubricating oil by using as the lubricating oil a
formulated oil including a lubricating oil base stock as a major
component and a coupled block copolymer as a minor component. A
lubricating engine oil including a lubricating oil base stock as a
major component and a coupled block copolymer as a minor
component.
Inventors: |
Eirich; Benjamin D.;
(Wenonah, NJ) ; Deckman; Douglas Edward; (Mullica
Hill, NJ) ; Patil; Abhimanyu Onkar; (Westfield,
NJ) ; Habeeb; Jacob Joseph; (Jamul, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Eirich; Benjamin D.
Deckman; Douglas Edward
Patil; Abhimanyu Onkar
Habeeb; Jacob Joseph |
Wenonah
Mullica Hill
Westfield
Jamul |
NJ
NJ
NJ
CA |
US
US
US
US |
|
|
Assignee: |
ExxonMobil Research and Engineering
Company
Annandale
NJ
|
Family ID: |
50382553 |
Appl. No.: |
14/189565 |
Filed: |
February 25, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61783192 |
Mar 14, 2013 |
|
|
|
Current U.S.
Class: |
508/287 ;
508/304; 508/562 |
Current CPC
Class: |
C10M 2209/1033 20130101;
C10M 2209/103 20130101; C10M 145/26 20130101; C10N 2030/24
20200501; C10M 2223/045 20130101; C10M 2217/041 20130101; C10M
2207/028 20130101; C10N 2030/36 20200501; C10M 145/18 20130101;
C10M 2205/028 20130101; C10N 2040/25 20130101; C10M 2205/0285
20130101; C10M 2219/046 20130101; C10M 2207/262 20130101; C10M
2203/1006 20130101; C10N 2030/10 20130101; C10M 2209/108 20130101;
C10M 2215/086 20130101; C10M 2205/028 20130101; C10M 2209/103
20130101 |
Class at
Publication: |
508/287 ;
508/562; 508/304 |
International
Class: |
C10M 149/22 20060101
C10M149/22; C10M 141/08 20060101 C10M141/08; C10M 141/10 20060101
C10M141/10 |
Claims
1. A method selected from: (a) a method for improving the ability
of an engine lubricating oil contaminated with water and fuel to
emulsify water contamination by using as the engine lubricating oil
a formulated oil comprising a lubricating oil base stock as a major
component and a coupled block copolymer as a minor component;
wherein the coupled block copolymer comprises: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols; wherein the end group of the polyether moiety is
different than the end group of the hydrocarbon moiety, and the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith; and wherein, in an engine lubricated with said
lubricating oil, the ability of the engine lubricating oil
contaminated with water and fuel to emulsify water contamination is
improved as compared to the ability of an engine lubricating oil
contaminated with water and fuel to emulsify water contamination
using a lubricating oil containing a minor component other than the
coupled block copolymer; and (b) a method for improving
thermo-oxidative stability and elastomer compatibility in an engine
lubricated with a lubricating oil by using as the lubricating oil a
formulated oil comprising a lubricating oil base stock as a major
component and a coupled block copolymer as a minor component;
wherein the coupled block copolymer comprises: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols; wherein the end group of the polyether moiety is
different than the end group of the hydrocarbon moiety, and the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith; and wherein, in an engine lubricated with said
lubricating oil, thermo-oxidative stability and elastomer
compatibility are improved as compared to thermo-oxidative
stability and elastomer compatibility achieved using a lubricating
oil containing a minor component other than the coupled block
copolymer.
2. The method of claim 1 wherein the lubricating oil base stock
comprises a Group I, II, III, IV or V base oil stock.
3. The method of claim 1 wherein the lubricating oil base stock
comprises a poly alpha olefin (PAO) base stock.
4. The method of claim 1 wherein the hydrocarbon moiety is a
poly-.alpha.-olefin and the polyether moiety is a polyalkylene
glycol, and wherein the poly-.alpha.-olefin is difunctional and the
polyalkylene glycol is difunctional.
5. The method of claim 4 wherein the polyalkylene glycol is a
Jeffamine.RTM. polyetheramine, and wherein the Jeffamine.RTM.
polyetheramine is at least one amine selected from the group
consisting of: poly(propyleneglycol) bis(2-aminopropylether), and
poly(propyleneglycol)-block-poly(ethyleneglycol-block
poly(propyleneglycol) bis(2-aminopropylether).
6. The method of claim 1 wherein the hydrocarbon moiety is an alkyl
glycidyl ether, Armeen.RTM. amine or dioctylamine.
7. The method of claim 1 wherein the block copolymer comprises a
diblock copolymer or a repeating diblock copolymer, and wherein the
block copolymer has an average molecular weight of 200 to
20000.
8. The method of claim 1 wherein the coupled block copolymer is
present in an amount sufficient for the lubricating oil to pass
ILSAC GF-5 specification and/or ASTM D7563, or wherein the ability
of the engine lubricating oil to emulsify water and fuel as
measured by ASTM D7563 shows no observable aqueous layer.
9. The method of claim 1 wherein the lubricating oil base stock is
present in an amount of 50 to 90 wt % of the lubricant composition,
and the coupled block copolymer is present in an amount of 1 to 10
wt % of the lubricant composition.
10. The method of claim 1 wherein the lubricating oil further
comprises one or more of a viscosity improver, antioxidant, ashless
antioxidant, antiwear, detergent, dispersant, pour point
depressant, corrosion inhibitor, metal deactivator, seal
compatibility additive, anti-foam agent, inhibitor, and anti-rust
additive.
11. A lubricating engine oil selected from: (a) a lubricating
engine oil comprising a lubricating oil base stock as a major
component and a coupled block copolymer as a minor component;
wherein the coupled block copolymer comprises: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols; wherein the end group of the polyether moiety is
different than the end group of the hydrocarbon moiety, and wherein
the hydrocarbon moiety and the polyether moiety are copolymerizable
therewith; and wherein, in an engine lubricated with said
lubricating oil, the ability of the engine lubricating oil
contaminated with water and fuel to emulsify water contamination is
improved as compared to the ability of an engine lubricating oil
contaminated with water and fuel to emulsify water contamination
using a lubricating oil containing a minor component other than the
coupled block copolymer; and (b) a lubricating engine oil
comprising a lubricating oil base stock as a major component and a
coupled block copolymer as a minor component; wherein the coupled
block copolymer comprises: an "A" block of a functionalized
hydrocarbon moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols; and a "B" block of a functionalized polyether
moiety including one or more functional end groups derived from:
epoxides, amines, acids, acid chlorides, acid anhydrides, halogens,
vinyl or vinylidene double bonds, aromatic rings or thiols; wherein
the end group of the polyether moiety is different than the end
group of the hydrocarbon moiety, and wherein the hydrocarbon moiety
and the polyether moiety are copolymerizable therewith; and
wherein, in an engine lubricated with said lubricating oil,
thernmo-oxidative stability and elastomer compatibility are
improved as compared to thermo-oxidative stability and elastomer
compatibility achieved using a lubricating oil containing a minor
component other than the coupled block copolymer.
12. The lubricating engine oil of claim 11 wherein the lubricating
oil base stock comprises a Group I, II, III, IV or V base oil
stock.
13. The lubricating engine oil of claim 11 wherein the lubricating
oil base stock comprises a poly alpha olefin (PAO) base stock.
14. The lubricating engine oil of claim 11 wherein the hydrocarbon
moiety is a poly-.alpha.-olefin and the polyether moiety is a
polyalkylene glycol, and wherein the polyalkylene glycol is
difunctional and the poly-.alpha.-olefin is difunctional.
15. The lubricating engine oil of claim 14 wherein the polyalkylene
glycol is a Jeffamine.RTM. polyetheramine, and wherein the
Jeffamine.RTM. polyetheramine is at least one amine selected from
the group consisting of: poly(propyleneglycol)
bis(2-aminopropylether), and
poly(propyleneglycol)-block-poly(ethyleneglycol-block
poly(propyleneglycol) bis(2-aminopropylether).
16. The lubricating engine oil of claim 11 wherein the hydrocarbon
moiety is an alkyl glycidyl ether, Armeen.RTM. amine or
dioctylamine.
17. The lubricating engine oil of claim 11 wherein the block
copolymer comprises a diblock copolymer or a repeating diblock
copolymer, and wherein the block copolymer has an average molecular
weight of 200 to 20000.
18. The lubricating engine oil of claim 11 wherein the coupled
block copolymer is present in an amount sufficient for the
lubricating oil to pass ILSAC GF-5 specification and/or ASTM D7563,
or wherein the ability of the engine lubricating oil to emulsify
water and fuel as measured by ASTM D7563 shows no observable
aqueous layer.
19. The lubricating engine oil of claim 11 wherein the lubricating
oil base stock is present in an amount of 50 to 80 wt % of the
lubricant composition, and the coupled block copolymer is present
in an amount of 1 to 10 wt % of the lubricant composition.
20. The lubricating engine oil of claim 11 wherein the lubricating
oil further comprises one or more of a viscosity improver,
antioxidant, ashless antioxidant, antiwear, detergent, dispersant,
pour point depressant, corrosion inhibitor, metal deactivator, seal
compatibility additive, anti-foam agent, inhibitor, and anti-rust
additive.
21. The method of claim 10 wherein the lubricating oil comprises a
lubricating oil base stock selected from a Group I, II, III, IV or
V base oil stock, a poly-.alpha.-olefin (PAO)-polyalkylene glycol
(PAG) coupled block copolymer, a salicylate, sulfonate or phenate
based detergent, an ashless antioxidant, a succinimide based
dispersant, a zinc dialkyldithiophosphate (ZDDP), a friction
modifier, a corrosion inhibitor, and a defoamant.
22. The lubricating engine oil of claim 20 which comprises a
lubricating oil base stock selected from a Group I, II, III, IV or
V base oil stock, a poly-.alpha.-olefin (PAO)-polyalkylene glycol
(PAG) coupled block copolymer, a salicylate, sulfonate or phenate
based detergent, an ashless antioxidant, a succinimide based
dispersant, a zinc dialkyldithiophosphate (ZDDP), a friction
modifier, a corrosion inhibitor, and a defoamant.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application Ser. No. 61/783,192 filed Mar. 14, 2013 and is herein
incorporated by reference in its entirety.
FIELD
[0002] This disclosure relates to lubricating engines using
formulated lubricating oils containing a coupled block copolymer
that are capable of emulsifying water contamination in a
lubricating oil as well as improving thermal-oxidative stability
and elastomer compatibility/manageability in an engine lubricated
with the lubricating oil.
BACKGROUND
[0003] Lubricants in commercial use today are prepared from a
variety of natural and synthetic base stocks admixed with various
additive packages and solvents depending upon their intended
application. The base stocks typically include mineral oils, poly
alpha olefins (PAO), gas-to-liquid base oils (GTL), silicone oils,
phosphate esters, diesters, polyol esters, and the like.
[0004] With the use of E85 fuels, in an internal combustion engine,
the engine oil can become contaminated with water and fuel. Phase
separation can occur, resulting in an aqueous layer and an oil
layer. This can affect the lubrication and detergency properties of
an engine oil.
[0005] To mitigate this issue, an engine oil should be capable of
emulsifying water contamination. A new standard test method was
introduced into the latest ILSAC GF-5 specification: Evaluation of
the Ability of Engine Oil to Emulsify Water and Simulated Ed85 Fuel
(ASTM D7563). This is a relatively new test method and there are no
specific additives developed that address emulsion characteristics
in engine oils. Pour Point Depressants (commonly polymethacrylates)
have found some application in controlling emulsion.
[0006] Therefore, there is a need for engine oil additives capable
of emulsifying water contamination in an engine oil so as to enable
the engine oil to pass the ILSAC GF-5 specification and ASTM D7563
test.
[0007] The present disclosure also provides many additional
advantages, which shall become apparent as described below.
SUMMARY
[0008] The lubricating oils of this disclosure exhibit
significantly improved emulsion characteristics, as measured by
ASTM D7563, in comparison with lubricating oils that do not contain
a coupled block copolymer. The lubricating oils of this disclosure
also exhibit improved thermal-oxidative stability and elastomer
compatibility/manageability in comparison with lubricating oils
that do not contain a coupled block copolymer. The coupled block
copolymer used in the lubricating oils of this disclosure imparts
desired emulsion characteristics to a lubricating oil contaminated
with water and fuel, and also imparts desired thermo-oxidative
stability and elastomer compatibility in an engine lubricated with
the lubricating oil.
[0009] This disclosure is directed in part to a method for
improving the ability of an engine lubricating oil contaminated
with water and fuel to emulsify water contamination by using as the
engine lubricating oil a formulated oil comprising a lubricating
oil base stock as a major component and a coupled block copolymer
as a minor component. The coupled block copolymer comprises: an "A"
block of a functionalized hydrocarbon moiety including one or more
functional end groups derived from: epoxides, amines, acids, acid
chlorides, acid anhydrides, halogens, vinyl or vinylidene double
bonds, aromatic rings or thiols; and a "B" block of a
functionalized polyether moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols. The end group of the polyether moiety is
different than the end group of the hydrocarbon moiety, and the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith. In an engine lubricated with said lubricating oil, the
ability of the engine lubricating oil contaminated with water and
fuel to emulsify water contamination is improved as compared to the
ability of an engine lubricating oil contaminated with water and
fuel to emulsify water contamination using a lubricating oil
containing a minor component other than the coupled block
copolymer.
[0010] This disclosure is also directed in part to a method for
improving thermo-oxidative stability and elastomer compatibility in
an engine lubricated with a lubricating oil by using as the
lubricating oil a formulated oil comprising a lubricating oil base
stock as a major component and a coupled block copolymer as a minor
component. The coupled block copolymer comprises: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols. The end group of the polyether moiety is different
than the end group of the hydrocarbon moiety, and the hydrocarbon
moiety and the polyether moiety are copolymerizable therewith. In
an engine lubricated with said lubricating oil, thermo-oxidative
stability and elastomer compatibility are improved as compared to
thermo-oxidative stability and elastomer compatibility achieved
using a lubricating oil containing a minor component other than the
coupled block copolymer.
[0011] This disclosure is further directed in part to a lubricating
engine oil comprising a lubricating oil base stock as a major
component and a coupled block copolymer as a minor component. The
coupled block copolymer comprises: an "A" block of a functionalized
hydrocarbon moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols; and a "B" block of a functionalized polyether
moiety including one or more functional end groups derived from:
epoxides, amines, acids, acid chlorides, acid anhydrides, halogens,
vinyl or vinylidene double bonds, aromatic rings or thiols. The end
group of the polyether moiety is different than the end group of
the hydrocarbon moiety, and wherein the hydrocarbon moiety and the
polyether moiety are copolymerizable therewith. In an engine
lubricated with said lubricating oil, the ability of the engine
lubricating oil contaminated with water and fuel to emulsify water
contamination is improved as compared to the ability of an engine
lubricating oil contaminated with water and fuel to emulsify water
contamination using a lubricating oil containing a minor component
other than the coupled block copolymer.
[0012] This disclosure is yet further directed in part to a
lubricating engine oil comprising a lubricating oil base stock as a
major component and a coupled block copolymer as a minor component.
The coupled block copolymer comprises: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols. The end group of the polyether moiety is different
than the end group of the hydrocarbon moiety, and wherein the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith. In an engine lubricated with said lubricating oil,
thermo-oxidative stability and elastomer compatibility are improved
as compared to thermo-oxidative stability and elastomer
compatibility achieved using a lubricating oil containing a minor
component other than the coupled block copolymer.
[0013] It has been surprisingly found that the lubricating oils
containing a coupled block copolymer in accordance with this
disclosure improve the ability of the engine lubricating oil
contaminated with water and fuel to emulsify water contamination as
compared to the ability of an engine lubricating oil contaminated
with water and fuel to emulsify water contamination using a
lubricating oil containing a minor component other than the coupled
block copolymer. In addition, it has been surprisingly found in an
engine lubricated with the lubricating oil of this disclosure,
thermo-oxidative stability and elastomer compatibility are improved
as compared to thermo-oxidative stability and elastomer
compatibility achieved using a lubricating oil containing a minor
component other than the coupled block copolymer.
[0014] Further objects, features and advantages of the present
disclosure will be understood by reference to the following
drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 graphically shows the results of the ASTM D7563 E85
emulsion testing. One test was conducted at 0.degree. C. and the
other test conducted at 25.degree. C. as shown in the Examples.
[0016] FIG. 2 graphically shows the results of Pressure
Differential Scanning Calorimetry (PDSC) at 210.degree. C. and 100
psi air. This test measures enthalpy change over time as shown in
the Examples. The point at which a significant exotherm occurs is
considered the induction time. A greater resistance to oxidation
induction is desirable.
[0017] FIG. 3 lists the results of elastomer compatability
performance testing for four Association des Constructucteurs
Europeens D'Automobiles (ACEA) elastomers (i.e., Viton, Acrylate,
Silicone, and Nitrile) as shown in the Examples.
DETAILED DESCRIPTION
[0018] All numerical values within the detailed description and the
claims herein are modified by "about" or "approximately" the
indicated value, and take into account experimental error and
variations that would be expected by a person having ordinary skill
in the art.
[0019] This disclosure provides lubricating oils useful as engine
oils and in other applications characterized by an ability to
emulsify water contamination in the lubricating oil. This
disclosure provides lubricating oils useful as engine oils and in
other applications characterized by an excellent balance of
thermo-oxidative stability and elastomer compatibility in an engine
lubricated with the lubricating oil. The lubricating oils are based
on high quality base stocks including a major portion of a
hydrocarbon base fluid such as a PAO or GTL with a secondary base
stock component which is preferably a coupled block copolymer. In
the present specification and claims, the terms base oil(s) and
base stock(s) are used interchangeably.
Lubricating Oil Base Stocks
[0020] A wide range of lubricating oils is known in the art.
Lubricating oils that are useful in the present disclosure are both
natural oils and synthetic oils. Natural and synthetic oils (or
mixtures thereof) can be used unrefined, refined, or rerefined (the
latter is also known as reclaimed or reprocessed oil). Unrefined
oils are those obtained directly from a natural or synthetic source
and used without added purification. These include shale oil
obtained directly from retorting operations, petroleum oil obtained
directly from primary distillation, and ester oil obtained directly
from an esterification process. Refined oils are similar to the
oils discussed for unrefined oils except refined oils are subjected
to one or more purification steps to improve the at least one
lubricating oil property. One skilled in the art is familiar with
many purification processes. These processes include solvent
extraction, secondary distillation, acid extraction, base
extraction, filtration, and percolation. Rerefined oils are
obtained by processes analogous to refined oils but using an oil
that has been previously used as a feed stock.
[0021] 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 80 to 120 and contain greater than 0.03% sulfur
and less than 90% saturates. Group II base stocks generally have a
viscosity index of between 80 to 120, and contain less than or
equal to 0.03% sulfur and greater than or equal to 90% saturates.
Group III stock generally has a viscosity index greater than 120
and contains less than or equal to 0.03% sulfur and greater than
90% saturates. Group IV includes polyalphaolefins (PAO). Group V
base stocks include base stocks not included in Groups I-IV. The
table below summarizes properties of each of these five groups.
TABLE-US-00001 Base Oil Properties Saturates Sulfur Viscosity Index
Group I <90 and/or >0.03% and .gtoreq.80 and <120 Group II
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.80 and <120 Group III
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.120 Group IV All
polyalphaolefins (PAO) Group V All Stocks Not Included in Groups
I-IV
[0022] Natural oils include animal oils, vegetable oils (castor oil
and lard oil, for example), and mineral oils. Animal and vegetable
oils possessing favorable thermal oxidative stability can be used.
Of the natural oils, mineral oils are preferred. Mineral oils vary
widely as to their crude source, for example, as to whether they
are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils
derived from coal or shale are also useful in the present
disclosure. Natural oils vary also as to the method used for their
production and purification, for example, their distillation range
and whether they are straight run or cracked, hydrorefined, or
solvent extracted.
[0023] Group II and/or Group III hydroprocessed or hydrocracked
base stocks, as well as synthetic oils such as polyalphaolefins,
alkyl aromatics and synthetic esters, i.e. Group IV and Group V
oils are also well known base stock oils. The Group III base stock
is highly paraffinic with saturates level higher than 90%,
preferably 95%, a viscosity index greater than 125, preferably
greater than 135, or more preferably greater than 140, very low
aromatics of 3%, preferably less than 1%, and aniline point of 118
or higher.
[0024] Synthetic oils include hydrocarbon oil such as polymerized
and interpolymerized olefins (polybutylenes, polypropylenes,
propylene isobutylene copolymers, ethylene-olefin copolymers, and
ethylene-alphaolefin copolymers, for example). Polyalphaolefin
(PAO) oil base stocks, the Group IV API base stocks, are a commonly
used synthetic hydrocarbon oil. By way of example, PAOs derived
from C.sub.6, C.sub.8, C.sub.10, C.sub.12, C.sub.14, C.sub.16
olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.
4,956,122; 4,827,064: and 4,827,073, which are incorporated herein
by reference in their entirety. Group IV oils, that is, the PAO
base stocks have viscosity indices preferably greater than 130,
more preferably greater than 135, still more preferably greater
than 140.
[0025] PAOs are a class of hydrocarbons that can be manufactured by
the catalytic oligomerization (polymerization to
low-molecular-weight products) of linear .alpha.-olefin (LAO)
monomers. These typically range from 1-octene to 1-dodecene, or
1-octene to 1-tetradecene, with 1-decene being a preferred
material, although oligomeric copolymers of lower olefins such as
ethylene and propylene may also be used, including copolymers of
ethylene with higher olefins as described in U.S. Pat. No.
4,956,122 and the patents referred to therein, all of which are
incorporated by reference in their entireties. PAO products have
achieved importance in the lubricating oil market. Typically there
are two classes of synthetic hydrocarbon fluids (SHF) produced from
linear alpha-olefins, the two classes of SHF being denoted as PAO
and HVI-PAO (high viscosity index PAO's). PAO's of different
viscosity grades are typically produced using promoted BF.sub.3 or
AlCl.sub.3 catalysts.
[0026] Specifically, PAOs may be produced by the polymerization of
olefin feed in the presence of a catalyst, such as AlCl.sub.3,
BF.sub.3, or promoted AlCl.sub.3 or BF.sub.3. Processes for the
production of PAOs are disclosed, for example, in the following
patents: U.S. Pat. Nos. 3,149,178; 3,382,291; 3,742,082; 3,769,363;
3,780,128; 4,172,855 and 4,956,122, which are fully incorporated
herein by reference. PAOs are also discussed in the following:
Will, J. G. Lubrication Fundamentals, Marcel Dekker: New York,
1980. Subsequent to polymerization, the PAO lubricant range
products are typically hydrogenated in order to reduce the residual
unsaturation, generally to a level of greater than 90% of
hydrogenation. High viscosity PAO's may be conveniently made by the
polymerization of an alpha-olefin in the presence of a
polymerization catalyst such as Friedel-Crafts catalysts. These
include, for example, boron trifluoride, aluminum trichloride, or
boron trifluoride, promoted with water, with alcohols such as
ethanol, propanol, or butanol, with carboxylic acids, or with
esters such as ethyl acetate or ethyl propionate or ether such as
diethyl ether, and diisopropyl ether. (See for example, the methods
disclosed by U.S. Pat. Nos. 4,149,178 and 3,382,291.) Other
descriptions of PAO synthesis are found in the following: U.S. Pat.
No. 3,742,082; U.S. Pat. No. 3,769,363; U.S. Pat. No. 3,876,720;
U.S. Pat. No. 4,239,930: U.S. Pat. No. 4,367,352; U.S. Pat. No.
4,413,156; U.S. Pat. No. 4,434,408; U.S. Pat. No. 4,910,355; U.S.
Pat. No. 4,956,122; and U.S. Pat. No. 5,068,487, all of which are
incorporated in their entirety herein by reference.
[0027] Another class of HVI-PAOs may be prepared by the action of a
supported, reduced chromium catalyst with an alpha-olefin monomer.
Such PAOs are described in U.S. Pat. No. 4,827,073; U.S. Pat. No.
4,827,064; U.S. Pat. No. 4,967,032; U.S. Pat. No. 4,926,004; and
U.S. Pat. No. 4,914,254. Commercially available PAOs include
SpectraSyn.TM. 2, 4, 5, 6, 8, 10, 40, 100 and SpectraSyn Ultra.TM.
150, SpectraSyn Ultra.TM. 300, SpectraSyn Ultra.TM. 1000, etc.
(ExxonMobil Chemical Company, Houston, Tex.). Also included are
PAOs prepared the presence of a metallocene catalyst with a
non-coordinating anion activator and hydrogen as discussed in U.S.
Published Patent Application No. 2008/0177121.
[0028] Esters in a minor amount may be useful in the lubricating
oils of this disclosure. Additive solvency and seal compatibility
characteristics may be secured by the use of esters such as the
esters of dibasic acids with monoalkanols and the polyol esters of
monocarboxylic acids. Esters of the former type include, for
example, the esters of dicarboxylic acids such as phthalic acid,
succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid,
etc., with a variety of alcohols such as butyl alcohol, hexyl
alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specific
examples of these types of esters include dibutyl adipate,
di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, etc.
[0029] Particularly useful synthetic esters are those which are
obtained by reacting one or more polyhydric alcohols, preferably
the hindered polyols such as the neopentyl polyols; e.g., neopentyl
glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,
trimethylol propane, pentaerythritol and dipentaerythritol with
alkanoic acids containing at least 4 carbon atoms, preferably
C.sub.5 to C.sub.30 acids such as saturated straight chain fatty
acids including caprylic acid, capric acids, lauric acid, myristic
acid, palmitic acid, stearic acid, arachic acid, and behenic acid,
or the corresponding branched chain fatty acids or unsaturated
fatty acids such as oleic acid, or mixtures of any of these
materials.
[0030] Esters should be used in a amount such that the improved
wear and corrosion resistance provided by the lubricating oils of
this disclosure are not adversely affected. The esters preferably
have a D5293 viscosity of less than 10,000 cP at -35.degree. C.
[0031] Non-conventional or unconventional base stocks and/or base
oils include one or a mixture of base stock(s) and/or base oil(s)
derived from: (1) one or more Gas-to-Liquids (GTL) materials, as
well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent)
dewaxed base stock(s) and/or base oils derived from synthetic wax,
natural wax or waxy feeds, mineral and/or non-mineral oil waxy feed
stocks such as gas oils, slack waxes (derived from the solvent
dewaxing of natural oils, mineral oils or synthetic oils; e.g.,
Fischer-Tropsch feed stocks), natural waxes, and waxy stocks such
as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate,
hydrocrackate, thermal crackates, foots oil or other mineral,
mineral oil, or even non-petroleum oil derived waxy materials such
as waxy materials recovered from coal liquefaction or shale oil,
linear or branched hydrocarbyl compounds with carbon number of or
greater, preferably 30 or greater and mixtures of such base stocks
and/or base oils.
[0032] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and/or base oils
are GTL materials of lubricating viscosity that are generally
derived from hydrocarbons; for example, waxy synthesized
hydrocarbons, that are themselves derived from simpler gaseous
carbon-containing compounds, hydrogen-containing compounds and/or
elements as feed stocks. GTL base stock(s) and/or base oil(s)
include oils boiling in the lube oil boiling range (1)
separated/fractionated from synthesized GTL materials such as, for
example, by distillation and subsequently subjected to a final wax
processing step which involves either or both of a catalytic
dewaxing process, or a solvent dewaxing process, to produce lube
oils of reduced/low pour point; (2) synthesized wax isomerates,
comprising, for example, hydrodewaxed or hydroisomerized cat and/or
solvent dewaxed synthesized wax or waxy hydrocarbons; (3)
hydrodewaxed or hydroisomerized cat and/or solvent dewaxed
Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); preferably
hydrodewaxed or hydroisomerized/followed by cat and/or solvent
dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T
waxes, or mixtures thereof.
[0033] GTL base stock(s) and/or base oil(s) derived from GTL
materials, especially, hydrodewaxed or hydroisomerized/followed by
cat and/or solvent dewaxed wax or waxy feed, preferably F-T
material derived base stock(s) and/or base oil(s), are
characterized typically as having kinematic viscosities at
100.degree. C. of from 2 mm.sup.2 is to 50 mm.sup.2/s (ASTM D445).
They are further characterized typically as having pour points of
-5.degree. C. to -40.degree. C. or lower (ASTM D97). They are also
characterized typically as having viscosity indices of 80 to 140 or
greater (ASTM D2270).
[0034] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) typically have very low sulfur and
nitrogen content, generally containing less than 10 ppm, and more
typically less than 5 ppm of each of these elements. The sulfur and
nitrogen content of GTL base stock(s) and/or base oil(s) obtained
from F-T material, especially F-T wax, is essentially nil. In
addition, the absence of phosphorous and aromatics make this
materially especially suitable for the formulation of low SAP
products.
[0035] The term GTL base stock and/or base oil and/or wax isomerate
base stock and/or base oil is to be understood as embracing
individual fractions of such materials of wide viscosity range as
recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low
viscosity fractions with one, two or more higher viscosity
fractions to produce a blend wherein the blend exhibits a target
kinematic viscosity.
[0036] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived is preferably an F-T material (i.e.,
hydrocarbons, waxy hydrocarbons, wax).
[0037] Base oils for use in the formulated lubricating oils useful
in the present disclosure are any of the variety of oils
corresponding to API Group I, Group II, Group III, Group IV and
Group V oils and mixtures thereof, preferably API Group II, Group
III, Group IV and Group V oils and mixtures thereof, more
preferably the Group III to Group V base oils due to their
exceptional volatility, stability, viscometric and cleanliness
features. Minor quantities of Group I stock, such as the amount
used to dilute additives for blending into formulated lube oil
products, can be tolerated but should be kept to a minimum, i.e.
amounts only associated with their use as diluent/carrier oil for
additives used on an "as-received" basis. Even in regard to the
Group II stocks, it is preferred that the Group II stock be in the
higher quality range associated with that stock, i.e. a Group II
stock having a viscosity index in the range 100<VI<120.
[0038] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) and hydrodewaxed, or
hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or
base oil(s) typically have very low sulfur and nitrogen content,
generally containing less than 10 ppm, and more typically less than
5 ppm of each of these elements. The sulfur and nitrogen content of
GTL base stock(s) and/or base oil(s) obtained from F-T material,
especially F-T wax, is essentially nil. In addition, the absence of
phosphorous and aromatics make this material especially suitable
for the formulation of low sulfur, sulfated ash, and phosphorus
(low SAP) products.
[0039] The basestock component of the present lubricating oils will
typically be from 50 to 90 weight percent of the total composition
(all proportions and percentages set out in this specification are
by weight unless the contrary is stated) and more usually in the
range of 55 to 85 weight percent.
Coupled PAO-PAG Block Copolymer Components
[0040] The coupled PAO-PAG block copolymer components useful in
this disclosure include those disclosed in U.S. Patent Application
Publication No. 2012/0115763, the disclosure of which is
incorporated herein by reference in its entirety.
[0041] The coupled PAO-PAG block copolymer components useful in
this disclosure can be prepared by copolymerizing a functionalized
hydrocarbon moiety and a functionalized polyether moiety, wherein
the functionalized hydrocarbon moiety includes one or more
functional end groups derived from: epoxides, amines, acids, acid
chlorides, acid anhydrides, halogens, vinyl or vinylidene double
bonds, aromatic rings or thiols, and wherein the functionalized
polyether moiety includes one or more functional end groups derived
from: epoxides, amines, acids, acid chlorides, acid anhydrides,
halogens, vinyl or vinylidene double bonds, aromatic rings or
thiols, wherein the end group of the polyether moiety is different
than the end group of the hydrocarbon moiety, and wherein the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith.
[0042] Preferably, the copolymerization takes place at a
temperature of 0.degree. C. to 200.degree. C., more preferably
between 20.degree. C. to 120.degree. C. The copolymerization takes
place for a time of 0.5 hours to 36 hours, more preferably between
1 hour to 24 hours.
[0043] A lubricant base stock that exhibits desirable performance
attributes due to the polymerization of a hydrocarbon moiety (e.g.,
poly-.alpha.-olefins (PAO)) having one or more functional end
groups and a polyether moiety (e.g., polyalkylene glycols (PAG))
having one or more functional end groups. More particular,
chemically coupled PAO-PAG block polymers of a hydrocarbon segment,
such as those of poly-.alpha.-olefin (PAO), and a polyether
segment, such as poly(alkylene glycol) (PAG), can be employed as
low molecular weight synthetic lubricant base stocks.
[0044] The hydrocarbon segment can be a long chain alkane, a
poly-.alpha.-olefin or a low molecular weight polyethylene,
propylene, polybutene, polyisobutylene or ethylene-.alpha.-olefin
macromer. The macromer is a unit having between 16 to 40 carbon
atoms derived from ethylene, propylene or .alpha.-olefins, and
combinations of the foregoing. The olefin monomeric units are
derived from one or more internal olefins. Alternatively, the
olefin monomeric units are derived from one or more olefins
including 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene. Still
further, the olefin monomeric unit is a low molecular weight
oligomer prepared via a metallocene catalytic reaction. The low
molecular weight oligomer is a dimer of 1-decene, 1-decene,
1-hexene, 1-tetradecene or mixtures thereof.
[0045] The polyether segment can be a polyalkylene glycol, such as
ethylene glycol, propylene glycol, polybutylene glycol, or
combinations thereof.
[0046] These segments are preferably coupled by chemical reaction
of functional groups that can be attached to either the hydrocarbon
segment and/or the polyether segment. Preferred schemes of coupling
reactions are depicted below:
##STR00001##
wherein X and Y are functional groups, such as amines, epoxides,
acids, acid halides, halides, alcohols, esters, ketones, vinyl or
vinylidene double bonds, substituted aromatic groups, phenols, and
thiols.
[0047] As one example, the PAO/PAG block copolymers substantially
maintain the respective benefits of both PAG and PAO fluids while
unexpectedly eliminating or diminishing their respective
disadvantages. Notably, the block copolymers provide surprisingly
superior step-out fuel economy and energy efficiency when used in
automotive engine lubricants and industrial and grease
lubricants.
[0048] Three reaction sequences are particularly preferred in
making the PAO-PAG block copolymers.
[0049] The first preferred sequence is the reaction of an alkyl
glycidyl ether with a Jeffamine.RTM. polyetheramine to obtain a
PAO-PAG block copolymer fluid.
##STR00002##
[0050] The PAO in above reaction is a C.sub.8/C.sub.10 alkyl
glycidyl ether wherein X is an epoxide and PAG is an polyether
amine (Jeffamine.RTM.) wherein Y is an amine.
[0051] The second preferred sequence is the reaction of an alkyl
epoxide (C.sub.20-epoxy) with a Jeffamine.RTM. polyetheramine to
obtain a PAO-PAG block copolymer fluid.
##STR00003##
[0052] The PAO-PAG shown above is similar to the structure depicted
in the first sequence except the PAO is a long chain alkyl group
(rather than a glycidyl ether) wherein X is an epoxide group and
PAG is a polyether amine (Jeffamine.RTM.) wherein Y is an amine
group.
[0053] The third preferred sequence is the reaction of a
poly(alkylene glycol) diglycidyl ether with an alkylamine to obtain
a PAO-PAG fluid.
##STR00004##
[0054] The PAO/PAG block copolymer shown above has a diepoxide as a
part of the polyether segment (PAG) and an amine as a part of
hydrocarbon (PAO) segment, wherein X is an epoxide group and Y is
an amine group.
[0055] Polyethylene glycol-containing diepoxides with dioctylamine
can be reacted to obtain a low molecular weight synthetic fluid.
For example, poly(ethyleneglycol) diglycidyl ether (MW of 526) and
dioctylamine can be reacted to obtain a liquid product that has
excellent lube properties like PAO. Besides poly(ethyleneglycol)
diglycidyl ether, other diepoxides that contain polyether segments
can be reacted with amines. Further, Armeen.RTM. amines other than
dioctylamine can be reacted with epoxides.
[0056] Epoxides can be prepared by epoxidation of unhydrogenated
PAO (PAO with terminal double bond) or of other hydrocarbon
macromers, such as polyethylene (PE), polypropylene (PP), ethylene
propylene (EP), ethylene butylene (EB), polyisobutylene (PIB),
poly-n-butylene (PNB) macromers, or of alkyl glycidyl ethers.
[0057] The macromer is a having between 16 to 40 carbon atoms
derived from ethylene, propylene, or .alpha.-olefins, and
combinations of the foregoing. The olefin monomeric units are
derived from one or more internal olefins. Alternatively, the
olefin monomeric units are derived from one or more olefins
including 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tetradecene, or 1-octadecene. Still further, the
olefin monomeric unit is a low molecular weight oligomer prepared
via a metallocene catalytic reaction. The low molecular weight
oligomer is a dimer of 1-decene, 1-decene, 1-hexene, 1-tetradecene
or mixtures thereof.
[0058] Olefins are epoxidized using an epoxidation catalyst to
produce a terminally epoxidized macromer. Epoxidation of the
present olefin materials can be affected using a peracid, such as
performic acid, perbenzoic acid or m-chloroperbenzoic acid, as the
oxidizing agent. The oxidation reaction can be performed using a
preformed peracid to affect the epoxidation, or the peracid can be
generated in-situ, for example by the addition of formic acid and
hydrogen peroxide to produce performic acid. Formic acid can be
added in a molar ratio to the olefin double bonds of from 10:1 to
30:1. Hydrogen peroxide can be added to the reaction mixture in a
molar ratio to the olefin double bonds of from 1.01:1 to 5:1.
Addition of both formic acid and H.sub.2O.sub.2 to the reaction
mixture results in the in situ formation of performic acid as an
epoxidizing agent. Typically, the epoxidation is conducted at a
temperature ranging from 25.degree. C. to 100.degree. C.,
preferably from 30.degree. C. to 70.degree. C. Suitable reaction
times will generally range from 0.1 hour to 36 hours, such as from
1 hour to 24 hours. Epoxidation reactions can provide conversion
from 50 to 100% of the double bonds into oxirane groups.
[0059] The epoxidation reaction is generally carried out in a
liquid reaction medium. The reaction medium can comprise only the
reactants essentially utilized in the process. More conventionally,
however, the liquid reaction medium will comprise a suitable
reaction solvent in which the reactants and catalyst materials can
be dissolved, suspended or dispersed. Suitable reaction solvents
include organic liquids which are inert in the reaction mixture. By
"inert" is meant that the solvent does not deleteriously affect the
oxidation reaction. Suitable inert organic solvents include
aromatic hydrocarbons such as benzene, toluene, xylenes,
benzonitrile, nitrobenzene, anisole, and phenyl nonane; saturated
aliphatic hydrocarbons having from 5 to 20 carbons, such as
pentane, hexane, and heptane; adiponitrile; halogenated
hydrocarbons such as methylene chloride, 1,2-dichloroethane,
chloroform, carbon tetrachloride and the like; non-fluorinated,
substituted saturated aliphatic and/or aromatic hydrocarbons having
from 1 to 20 carbons, including those selected from the group
consisting of alcohols such as methanol, propanol, butanol,
isopropanol, and 2,4-di-t-butylphenol; ketones such as acetone;
carboxylic acids such as propanoic acid and acetic acid; esters
such as ethyl acetate, ethyl benzoate, dimethyl succinate, butyl
acetate, tri-n-butyl phosphate, and dimethyl phthalate; ethers,
such as tetraglyme; and mixtures thereof.
[0060] One type of epoxidation of olefins involves reaction of the
material with a peracid, such as performic acid or
m-chloroperbenzoic acid, to provide an epoxidized material having
oxirane rings formed at the sites of the residual double bonds
within the molecule. Catalytic epoxidation alternatives using
hydrogen peroxide as an oxidizing agent instead of peracids can be
used to epoxidize some unsaturated materials. Catalysts based on
the use of high valent (d0), mostly Ti, V, Mo, W, and Re, metal
complexes are known to promote alkene epoxidation with
H.sub.2O.sub.2. Some notable effective epoxidation catalysts for
use with hydrogen peroxide include titanium silicates,
peroxophosphotungstates, manganese triazocyclononane, and
methylrhenium trioxide.
[0061] A poly-.alpha.-olefin-polyalkyleneglycol (PAO-PAG) type
fluid can be synthesized from a reaction of an alkyl epoxide
(C.sub.20-epoxy) with a polyether amine. Polyether amines, such as
the Jeffamine.RTM. polyetheramines, can be reacted with an epoxide
terminated hydrocarbon molecule (PAO-epoxide or C.sub.20-epoxy) to
obtain a low molecular weight synthetic fluid that can be used as
synthetic base stock.
[0062] The Jeffamine.RTM. polyetheramines can be amine-terminated
polyethers. The reaction of amine-terminated polyethers and
epoxides can be carried out neat or in solvents like THF, MEK or
ethanol. The temperature of the reaction can be 25.degree. C. to
60.degree. C. or higher. The reaction time can be a few hours to
few days.
[0063] The Jeffamine.RTM. polyetheramines can be amine-terminated
polyethers such as polyethylene oxide (PEO), polypropylene oxide
(PPO) or combination of PEO/PPO copolymers. For example, some of
the commercial polyethers include: poly(ethyleneglycol)
bis(3-aminopropylether) (34901-14-9, mw 1500),
poly(propyleneglycol) bis(2-aminopropylether) (mw 230),
poly(propyleneglycol) bis(2-aminopropylether) (mw 400),
poly(propyleneglycol) bis(2-aminopropylether) (9046-10-0, mw 2000),
poly(propyleneglycol) bis(2-aminopropylether) (mw 4000),
poly(propyleneglycol)-block-poly(ethyleneglycol)-block
poly(propyleneglycol) bis(2-aminopropylether) (65605-36-9)
(3.5:8.5) (PO:EO) (mw 600),
poly(propyleneglycol)-block-poly(ethyleneglycol)-block
poly(propyleneglycol) bis(2-aminopropylether) (3.5:15.5) (PO:EO)
(mw 900), poly(propyleneglycol)-block-poly(ethyleneglycol)-block
poly(propyleneglycol) bis(2-aminopropylether) (3.5:40.5) (PO:EO)
(mw 2000), glycerol tris[poly(propylene glycol), amine
terminated]ether (64852-22-8, mw 3000 or mw 440),
poly(tetrahydrofuran), bis(3-aminopropyl) terminated (72088-96-1),
and the like.
[0064] The chemical structures of examples of amine-terminated
polyethers are shown below:
##STR00005##
[0065] Jeffamine.RTM. polyetheramines can be monoamines that are
prepared by reaction of a monohydric alcohol initiator with
ethylene and/or propylene oxide, followed by conversion of the
resulting terminal hydroxyl group to an amine. These products are
produced by Huntsman as Jeffamine.RTM. monoamines (M series).
##STR00006##
[0066] The molecular weights of the product can be 600, 1000,
etc.
[0067] In this case, the sequence is the reaction of an alkyl
epoxide or alkyl diepoxide with monoamine polyether to obtain a
PAO-PAG fluid.
##STR00007##
[0068] The reaction of amine-terminated polyethers and epoxides can
be carried out neat or in solvents like THF, MEK or ethanol. The
temperature of the reaction can be 25.degree. C. to 60.degree. C.
or higher. The reaction time can be a few hours to few days.
[0069] The chemically coupled macromolecules of the present
disclosure is useful as a lubricant base stock or a functional
fluid and preferably has a 100.degree. C. kinematic viscosity of
1.5 cSt to 3000 cSt according to the ASTM D445 method. The
copolymer has a 40.degree. C. kinematic viscosity of 3 to 15000
cSt. Preferred polymers exhibit a high viscosity index (VI). The VI
typically ranges from 70 to 300 depending on viscosity, amount of
hydrocarbon segment units, amount of alkylene oxide units, type of
hydrocarbon segment or alkylene oxide units, method of synthesis,
chemical compositions, and the like. Pour points are generally
below -5.degree. C. even in the case of the higher molecular weight
oligomers with viscosities (100.degree. C.) of 20 cSt or higher.
Pour points (ASTM D97 or equivalent) generally range between -20
and -55.degree. C. and usually below -25.degree. C. Product
viscosity may vary in view of factors such as polymerization
conditions reaction temperature and reaction time. The lubricant
fraction of the product will typically be a material having a
viscosity between 4 cSt to 3000 cSt (at 100.degree. C.), but lower
viscosity products between 1.5 cSt to 40 cSt (at 100.degree. C.)
may also be obtained for use in lubricants in which a low viscosity
base stock is desired.
[0070] The molecular weight of the polymer typically ranges from
200 to 20,000, typically from 300 to 10,000, and most typically
from 350 to 7,500. Higher molecular weights and corresponding
viscosities may be achieved by suitable choice of starting
hydrocarbon segment, polyether segment and number of functional
groups and reaction conditions. Values of the polydispersity index
(PDI) are typically from 1.5 to 3.0, but can range from 1.01 to
6.
[0071] The polymer can take the form of a block copolymer or
multi-blocks or dendritic or star type or combination of those. The
polymer optionally may contain minor amounts of unreacted
hydrocarbon segment or polyether segment as long as a homogeneous
mixture can be obtained.
[0072] For automotive engine lubricant formulations, it is
generally preferred to have lower viscosity fluids, e.g., below 10
cSt at 100.degree. C. Lower viscosity is known to impart lower
viscous drag thus offering better energy efficiency or fuel
economy. Both low viscosity and high viscosity fluids are useful in
industrial lubricant formulations to yield different ISO vis grad
lubricants. For industrial lubricant formulations, it is generally
important to use fluids of high VI and high hydrolytic
stability.
[0073] For both engine and industrial lubricant application, it is
important to have a lubricant formulation with a low friction
coefficient. Generally fluids with low friction coefficients
exhibit low frictional loss during lubrication and fluids with high
friction coefficients exhibit high frictional loss during
lubrication. Low frictional loss is critical for improved energy or
fuel efficiency of formulated lubricants.
[0074] Friction coefficients can be measured by a High Frequency
Reciprocating Rig (HFRR) test. The test equipment and procedure are
similar to the ASTM D6079 method except the test oil temperature is
raised from 32.degree. C. to 195.degree. C. at 2.degree. C./minute,
400 g load, 60 Hz frequency. The test can measure average friction
coefficient and wear volume.
[0075] The PAO-PAG copolymers may take any form of block copolymer,
such as diblock, repeating block, and the like.
[0076] Other teachings to useful PAO and PAG fluids and processes
for making are disclosed in Synthetics, Mineral Oils, and Bio-Based
Lubricants, Chemistry and Technology, by L. R. Rudnick, CRC Press,
.COPYRGT.2006.
[0077] PAO-PAG fluids formed by combining a PAO type structure with
a PAG structure maintain the benefits of both PAO (good VI, PP, and
miscibility) and PAG (low friction coefficient) fluids. The fluids
are very good lubricant base stocks. The fluids are soluble in
hydrocarbon fluids. Thus, these fluids can be used along with other
base stocks, such as poly-.alpha.-olefins, Group III+ type fluids
(Visom, GTL, etc) and Group I-III base stocks.
Lubricant Compositions
[0078] The PAO-PAG block copolymer component useful in this
disclosure may be included in an engine oil formulation to yield
improved oxidative stability, wear resistance properties and
frictional properties. In one form of the present disclosure, a
lubricant composition for use in engine oil applications includes:
i) a first base stock selected from a Group I base stock, a Group
II base stock and a combination thereof at 50 to 80 wt % of the
lubricant composition, and ii) a block copolymer at 1 to 10 wt % of
the lubricant composition, including: an "A" block of a
functionalized hydrocarbon moiety including one or more functional
end groups derived from: epoxides, amines, acids, acid chlorides,
acid anhydrides, halogens, vinyl or vinylidene double bonds,
aromatic rings or thiols; and a "B" block of a functionalized
polyether moiety including one or more functional end groups
derived from: epoxides, amines, acids, acid chlorides, acid
anhydrides, halogens, vinyl or vinylidene double bonds, aromatic
rings or thiols, wherein the end group of the polyether moiety is
different than the end group of the hydrocarbon moiety, wherein the
hydrocarbon moiety and the polyether moiety are copolymerizable
therewith. Alternatively, the first base stock may be included at
55 to 75 wt %, or GO to 70 wt % of the lubricant formulation. In
one advantageous form, the first base stock is included at 73 wt %
of the lubricant composition and comprises 53 wt % of a Group I oil
and 20 wt % of a Group II oil.
[0079] Alternatively, the block copolymer fluid may be included at
1 to 8 wt %, or 3 to 6 wt % of the lubricant composition. In one
particularly advantageous form, the block copolymer fluid has a
hydrocarbon moiety of a poly-.alpha.-olefin and a polyether moiety
of a polyalkylene glycol and is included in the lubricant
composition at 3 wt %.
Other Additives
[0080] The formulated lubricating oil useful in the present
disclosure may additionally contain one or more of the other
commonly used lubricating oil performance additives including but
not limited to dispersants, other detergents, corrosion inhibitors,
rust inhibitors, metal deactivators, other anti-wear agents and/or
extreme pressure additives, anti-seizure agents, wax modifiers,
viscosity index improvers, viscosity modifiers, fluid-loss
additives, seal compatibility agents, other friction modifiers,
lubricity agents, anti-staining agents, chromophoric agents,
defoamants, demulsifiers, emulsifiers, densifiers, wetting agents,
gelling agents, tackiness agents, colorants, and others. For a
review of many commonly used additives, see Klamann in Lubricants
and Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN
0-89573-177-0. Reference is also made to "Lubricant Additives" by
M. W. Ranney, published by Noyes Data Corporation of Parkridge,
N.J. (1973).
[0081] The types and quantities of performance additives used in
combination with the instant disclosure in lubricant compositions
are not limited by the examples shown herein as illustrations.
Viscosity Modifiers/Improvers
[0082] The lubricant compositions disclosed herein may also include
one or more viscosity modifiers/viscosity improvers as part of the
lubricant composition. Viscosity modifiers (also known as Viscosity
Index modifiers, VI modifiers, Viscosity index improvers, and VI
improvers) increase the viscosity of the oil composition at
elevated temperatures which increases film thickness, while having
limited effect on viscosity at low temperatures.
[0083] Suitable viscosity improvers include high molecular weight
hydrocarbons, polyesters and viscosity index improver dispersants
that function as both a viscosity index improver and a dispersant.
Typical molecular weights of these polymers are between 10,000 to
1,000,000, more typically 20,000 to 500,000, and even more
typically between 50,000 and 200,000.
[0084] Examples of suitable viscosity improvers are polymers and
copolymers of methacrylate, butadiene, olefins, or alkylated
styrenes. Polyisobutylene is a commonly used viscosity index
improver. Another suitable viscosity index improver is
polymethacrylate (copolymers of various chain length alkyl
methacrylates, for example), some formulations of which also serve
as pour point depressants. Other suitable viscosity index improvers
include copolymers of ethylene and propylene, hydrogenated block
copolymers of styrene and isoprene, and polyacrylates (copolymers
of various chain length acrylates, for example). Specific examples
include styrene-isoprene or styrene-butadiene based polymers of
50,000 to 200,000 molecular weight.
[0085] The amount of viscosity modifier may range from zero to 25
wt %, or 0.2 to 20 wt %, or advantageously 3 to 15 wt %, or more
advantageously 5 to 13 wt %, or still more advantageously 6 to 10
wt %, based on active ingredient and depending on the specific
viscosity modifier used. In one particularly advantageous form, the
viscosity modifier is an olefin copolymer viscosity modifier at 3
to 15 wt %, or 5 to 13 wt %, or 6 to 10 wt % of the lubricant
composition. In one particularly advantageous form, the lubricant
compositions disclosed herein include 6 to 7 wt % of an olefin
copolymer viscosity modifier.
Additive Package
[0086] The lubricant compositions disclosed herein may also include
an additive package including a combination of antioxidants,
dispersants, detergents and antiwear agents. Further details on
these additives are included below. The additive package may be
included in the lubricant compositions at from 2 to 30 wt. %, 10 to
25 wt %, or 13 to 23 wt %, or 15 to 20 wt % of the lubricant
composition. In one particularly advantageous form, the additive
package is included at 17 wt % of the lubricant composition. One
non-limiting exemplary additive package that includes the above
combination of additives is supplied by Infineum and is designated
Infineum D3426.
Second Base Stock In addition to the first base stock and the
PAO-PAG block copolymer component, the lubricant compositions
disclosed herein may include a second base stock selected from a
metallocene poly-.alpha.-olefin, a poly-.alpha.-olefin, a GTL base
stock, and a Group III base stock. The second base stock may be
included in the lubricant composition at from 5 to 45 wt %, or 10
to 40 wt %, or 15 to 35 wt %, or 20 to 30 wt %.
Antioxidants
[0087] Typical antioxidant include phenolic antioxidants, aminic
antioxidants and oil-soluble copper complexes.
[0088] The phenolic antioxidants include sulfurized and
non-sulfurized phenolic antioxidants. The terms "phenolic type" or
"phenolic antioxidant" used herein includes compounds having one or
more than one hydroxyl group bound to an aromatic ring which may
itself be mononuclear, e.g., benzyl, or poly-nuclear, e.g.,
naphthyl and spiro aromatic compounds. Thus "phenol type" includes
phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc.,
as well as alkyl or alkenyl and sulfurized alkyl or alkenyl
derivatives thereof, and bisphenol type compounds including such
bi-phenol compounds linked by alkylene bridges sulfuric bridges or
oxygen bridges. Alkyl phenols include mono- and poly-alkyl or
alkenyl phenols, the alkyl or alkenyl group containing from 3-100
carbons, preferably 4 to 50 carbons and sulfurized derivatives
thereof, the number of alkyl or alkenyl groups present in the
aromatic ring ranging from 1 to up to the available unsatisfied
valences of the aromatic ring remaining after counting the number
of hydroxyl groups bound to the aromatic ring.
[0089] Generally, therefore, the phenolic anti-oxidant may be
represented by the general formula:
(R).sub.x--Ar--(OH).sub.y
where Ar is selected from the group consisting of:
##STR00008##
wherein R is a C.sub.3-C.sub.100 alkyl or alkenyl group, a sulfur
substituted alkyl or alkenyl group, preferably a C.sub.4-C.sub.50
alkyl or alkenyl group or sulfur substituted alkyl or alkenyl
group, more preferably C.sub.3-C.sub.100 alkyl or sulfur
substituted alkyl group, most preferably a C.sub.4-C.sub.50 alkyl
group, R.sup.g is a C.sub.1-C.sub.100 alkylene or sulfur
substituted alkylene group, preferably a C.sub.2-C.sub.50 alkylene
or sulfur substituted alkylene group, more preferably a
C.sub.2-C.sub.2 alkylene or sulfur substituted alkylene group, y is
at least 1 to up to the available valences of Ar, x ranges from 0
to up to the available valances of Ar-y, z ranges from 1 to 10, n
ranges from 0 to 20, and m is 0 to 4 and p is 0 or 1, preferably y
ranges from 1 to 3, x ranges from 0 to 3, z ranges from 1 to 4 and
n ranges from 0 to 5, and p is 0.
[0090] Preferred phenolic anti-oxidant compounds are the hindered
phenolics and phenolic esters which contain a sterically hindered
hydroxyl group, and these include those derivatives of dihydroxy
aryl compounds in which the hydroxyl groups are in the o- or
p-position to each other. Typical phenolic anti-oxidants include
the hindered phenols substituted with C.sub.1+ alkyl groups and the
alkylene coupled derivatives of these hindered phenols. Examples of
phenolic materials of this type 2-t-butyl-4-heptyl phenol;
2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;
2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;
2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl
phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl
phenol; and 2,6-di-t-butyl 4 alkoxy phenol; and
##STR00009##
[0091] Phenolic type antioxidants are well known in the lubricating
industry and commercial examples such as Ethanox.RTM. 4710,
Irganox.RTM. 1076, Irganox.RTM. L1035, Irganox.RTM. 1010,
Irganox.RTM. L109. Irganox.RTM. L118, Irganox.RTM. L135 and the
like are familiar to those skilled in the art. The above is
presented only by way of exemplification, not limitation on the
type of phenolic antioxidants which can be used.
[0092] The phenolic antioxidant can be employed in an amount in the
range of 0.1 to 3 wt %, preferably 0.25 to 2.5 wt %, more
preferably 0.5 to 2 wt % on an active ingredient basis.
[0093] Aromatic amine anti-oxidants include phenyl-.alpha.-naphthyl
amine which is described by the following molecular structure:
##STR00010##
wherein R.sup.z is hydrogen or a C.sub.1 to C.sub.14 linear or
C.sub.3 to C.sub.14 branched alkyl group, preferably C.sub.1 to
C.sub.10 linear or C.sub.3 to C.sub.10 branched alkyl group, more
preferably linear or branched C.sub.6 to C.sub.8 and n is an
integer ranging from 1 to 5 preferably 1. A particular example is
Irganox L06.
[0094] Other aromatic amine anti-oxidants include other alkylated
and non-alkylated aromatic amines such as aromatic monoamines of
the formula R.sup.8R.sup.9R.sup.10N where R.sup.8 is an aliphatic,
aromatic or substituted aromatic group, R.sup.9 is an aromatic or a
substituted aromatic group, and R.sup.10 is H, alkyl, aryl or
R.sup.11S(O).sub.xR.sup.12 where R.sup.11 is an alkylene,
alkenylene, or aralkylene group, R.sup.12 is a higher alkyl group,
or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The
aliphatic group R.sup.8 may contain from 1 to 20 carbon atoms, and
preferably contains from 6 to 12 carbon atoms. The aliphatic group
is a saturated aliphatic group. Preferably, both R.sup.8 and
R.sup.9 are aromatic or substituted aromatic groups, and the
aromatic group may be a fused ring aromatic group such as naphthyl.
Aromatic groups R.sup.8 and R.sup.9 may be joined together with
other groups such as S.
[0095] Typical aromatic amines antioxidants have alkyl substituent
groups of at least 6 carbon atoms. Examples of aliphatic groups
include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the
aliphatic groups will not contain more than 14 carbon atoms. The
general types of such other additional amine anti-oxidants which
may be present include diphenylamines, phenothiazines,
imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or
more of such other additional aromatic amines may also be present.
Polymeric amine antioxidants can also be used.
[0096] Another class of antioxidant used in lubricating oil
compositions and which may also be present are oil-soluble copper
compounds. Any oil-soluble suitable copper compound may be blended
into the lubricating oil. Examples of suitable copper antioxidants
include copper dihydrocarbyl thio- or dithiophosphates and copper
salts of carboxylic acid (naturally occurring or synthetic). Other
suitable copper salts include copper dithiacarbamates, sulphonates,
phenates, and acetylacetonates. Basic, neutral, or acidic copper
Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or
anhydrides are known to be particularly useful.
[0097] Such antioxidants may be used individually or as mixtures of
one or more types of antioxidants, the total amount employed being
an amount of 0.20 to 6 wt %, or 0.50 to 5 wt %, or 0.75 to 3 wt %
(on an as-received basis). Mixed ashless antioxidants are often
preferred, including those chosen from aminic antioxidants and
hindered phenolic antioxidants.
Detergents
[0098] In addition to the alkali or alkaline earth metal salicylate
detergent which is an optional component in the present disclosure,
other detergents may also be present. While such other detergents
can be present, it is preferred that the amount employed be such as
to not interfere with the synergistic effect attributable to the
presence of the salicylate. Therefore, most preferably such other
detergents are not employed.
[0099] If such additional detergents are present, they can include
alkali and alkaline earth metal phenates, sulfonates, carboxylates,
phosphonates and mixtures thereof. These supplemental detergents
can have total base number (TBN) ranging from neutral to highly
overbased, i.e. TBN of 0 to over 500, preferably 2 to 400, more
preferably 5 to 300, and they can be present either individually or
in combination with each other in an amount in the range of from 0
to 10 wt %, preferably 0.5 to 5 wt % (active ingredient) based on
the total weight of the formulated lubricating oil. Furthermore,
mixtures of neutral detergents and overbased detergents may be
useful.
[0100] Such additional other detergents include by way of example
and not limitation calcium phenates, calcium sulfonates, magnesium
phenates, magnesium sulfonates and other related components
(including borated detergents).
[0101] Another optional component of the present lubricant
compositions is one or more neutral/low TBN or mixture of
neutral/low TBN and overbased/high TBN alkali or alkaline earth
metal alkylsalicylate, sulfonate and/or phenate detergent
preferably neutral/low TBN alkali or alkaline earth metal
salicylate and at least one overbased/high TBN alkali or alkalene
earth metal salicylate or phenate, and optionally one or more
additional neutral and/or overbased alkali or alkaline earth metal
alkyl sulfonate, alkyl phenolate or alkylsalicylate detergent, the
detergent or detergent mixture being employed in the lubricant
composition in an amount sufficient to achieve a sulfated ash
content for the finished lubricant of 0.1 mass % to 2.0 mass %,
preferably 0.1 to 1.5 mass %, more preferably 0.1 to 1.0 mass %,
most preferably 0.1 to 0.7 mass %.
[0102] The TBN of the neutral/low TBN alkali or alkaline earth
metal alkyl salicylate, alkyl phenate or alkyl sulfonate is 150 or
less mg KOH/g of detergent, preferably 120 or less mg KOH/g, most
preferably 100 or less mg KOH/g while the TBN of the overbased/high
TBN alkali or alkaline earth metal alkyl salicylate, alkyl phenate
or alkyl sultanate is 160 or more mg KOH/g, preferably 190 or more
mg KOH/g, most preferably 250 or more mg KOH/g, TBN being measured
by ASTM D-2896.
[0103] The mixture of detergents may be added to the lubricant
composition in an amount up to 10 vol % based on active ingredient
in the detergent mixture, preferably in an amount up to 8 vol %
based on active ingredient, more preferably up to 6 vol % based on
active ingredient in the detergent mixture, most preferably between
1.5 to 5.0 vol %, based on active ingredient in the detergent
mixture.
[0104] By active ingredient is meant the amount of additive
actually constituting the name detergent or detergent mixture
chemicals in the formulation as received from the additive
supplier, less any diluent oil included in the material. Additives
are typically supplied by the manufacturer dissolved, suspended in
or mixed with diluent oil, usually a light oil, in order to provide
the additive in the more convenient liquid form. The active
ingredient in the mixture is the amount of actual desired chemical
in the material less the diluent oil.
Dispersants
[0105] During engine operation, oil-insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposition on metal surfaces. Dispersants
may be ashless or ash-forming in nature. Preferably, the dispersant
is ashless. So called ashless dispersants are organic materials
that form substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents
discussed above form ash upon combustion.
[0106] Suitable dispersants typically contain a polar group
attached to a relatively high molecular weight hydrocarbon chain.
The polar group typically contains at least one element of
nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain
50 to 400 carbon atoms.
[0107] A particularly useful class of dispersants are the
alkenylsuccinic derivatives, typically produced by the reaction of
a long chain substituted alkenyl succinic compound, usually a
substituted succinic anhydride, with a polyhydroxy or polyamino
compound. The long chain group constituting the oleophilic portion
of the molecule which confers solubility in the oil, is normally a
polyisobutylene group. Many examples of this type of dispersant are
well known commercially and in the literature. Exemplary U.S.
patents describing such dispersants are U.S. Pat. Nos. 3,172,892;
3,215,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607;
3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other
types of dispersant are described in U.S. Pat. Nos. 3,036,003;
3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804;
3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059;
3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300;
4,100,082; 5,705,458. A further description of dispersants may be
found, for example, in European Patent Application No. 471 071, to
which reference is made for this purpose.
[0108] Hydrocarbyl-substituted succinic acid compounds are popular
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound preferably having at
least 50 carbon atoms in the hydrocarbon substituent, with at least
one equivalent of an alkylene amine are particularly useful.
[0109] Succinimides are formed by the condensation reaction between
alkenyl succinic anhydrides and amines. Molar ratios can vary
depending on the amine or polyamine. For example, the molar ratio
of alkenyl succinic anhydride to TEPA can vary from 1:1 to 5:1.
[0110] Succinate esters are formed by the condensation reaction
between alkenyl succinic anhydrides and alcohols or polyols. Molar
ratios can vary depending on the alcohol or polyol used. For
example, the condensation product of an alkenyl succinic anhydride
and pentaerythritol is a useful dispersant.
[0111] Succinate ester amides are formed by condensation reaction
between alkenyl succinic anhydrides and alkanol amines. For
example, suitable alkanol amines include ethoxylated
polyalkylpolyamines, propoxylated polyalkylpolyamines and
polyalkenylpolyamines such as polyethylene polyamines. One example
is propoxylated hexamethylenediamine.
[0112] The molecular weight of the alkenyl succinic anhydrides will
typically range between 800 and 2,500. The above products can be
post-reacted with various reagents such as sulfur, oxygen,
formaldehyde, carboxylic acids such as oleic acid, and boron
compounds such as borate esters or highly borated dispersants. The
dispersants can be borated with from 0.1 to 5 moles of boron per
mole of dispersant reaction product.
[0113] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. Process aids and catalysts,
such as oleic acid and sulfonic acids, can also be part of the
reaction mixture. Molecular weights of the alkylphenols range from
800 to 2,500 or more.
[0114] Typical high molecular weight aliphatic acid modified
Mannich condensation products can be prepared from high molecular
weight alkyl-substituted hydroxyaromatics or HN(R).sub.2
group-containing reactants.
[0115] Examples of high molecular weight alkyl-substituted
hydroxyaromatic compounds are polypropylphenol, polybutylphenol,
and other polyalkylphenols. These polyalkylphenols can be obtained
by the alkylation, in the presence of an alkylating catalyst, such
as BF.sub.3, of phenol with high molecular weight polypropylene,
polybutylene, and other polyalkylene compounds to give alkyl
substituents on the benzene ring of phenol having an average
600-100,000 molecular weight.
[0116] Examples of HN(R).sub.2 group-containing reactants are
alkylene polyamines, principally polyethylene polyamines. Other
representative organic compounds containing at least one
HN(R).sub.2 group suitable for use in the preparation of Mannich
condensation products are well known and include the mono- and
di-amino alkanes and their substituted analogs, e.g., ethylamine
and diethanol amine; aromatic diamines. e.g., phenylene diamine,
diamino naphthalenes; heterocyclic amines, e.g., morpholine,
pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine;
melamine and their substituted analogs.
[0117] Examples of alkylene polyamine reactants include
ethylenediamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentaamine, pentaethylene hexamine, hexaethylene
heptaamine, heptaethylene octaamine, octaethylene nonaamine,
nonaethylene decamine, and decaethylene undecamine and mixture of
such amines having nitrogen contents corresponding to the alkylene
polyamines, in the formula H.sub.2N--(Z--NH--).sub.nH, mentioned
before, Z is a divalent ethylene and n is 1 to 10 of the foregoing
formula. Corresponding propylene polyamines such as propylene
diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta-
and hexaamines are also suitable reactants. The alkylene polyamines
are usually obtained by the reaction of ammonia and dihalo alkanes,
such as dichloro alkanes. Thus the alkylene polyamines obtained
from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of
dichloroalkanes having 2 to 6 carbon atoms and the chlorines on
different carbons are suitable alkylene polyamine reactants.
[0118] Aldehyde reactants useful in the preparation of the high
molecular products useful in this disclosure include the aliphatic
aldehydes such as formaldehyde (also as paraformaldehyde and
formalin), acetaldehyde and aldol (3-hydroxybutyraldehyde).
Formaldehyde or a formaldehyde-yielding reactant is preferred.
[0119] Preferred dispersants include borated and non-borated
succinimides, including those derivatives from mono-succinimides,
bis-succinimides, and/or mixtures of mono- and bis-succinimides,
wherein the hydrocarbyl succinimide is derived from a
hydrocarbylene group such as polyisobutylene having a Mn of from
500 to 5000 or more or a mixture of such hydrocarbylene groups.
Other preferred dispersants include succinic acid-esters and
amides, alkylphenol-polyamine-coupled Mannich adducts, their capped
derivatives, and other related components. Such additives may be
used in an amount of 0.1 to 20 wt %, preferably 0.1 to 8 wt %, more
preferably 1 to 6 wt % (on an as-received basis) based on the
weight of the total lubricant.
Pour Point Depressants
[0120] Conventional pour point depressants (also known as lube oil
flow improvers) may also be present. Pour point depressant may be
added to lower the minimum temperature at which the fluid will flow
or can be poured. Examples of suitable pour point depressants
include alkylated naphthalenes polymethacrylates, polyacrylates,
polyarylamides, condensation products of haloparaffin waxes and
aromatic compounds, vinyl carboxylate polymers, and terpolymers of
dialkylfumarates, vinyl esters of fatty acids and allyl vinyl
ethers. Such additives may be used in amount of 0.0 to 0.5 wt %,
preferably 0 to 0.3 wt %, more preferably 0.001 to 0.1 wt % on an
as-received basis.
Corrosion Inhibitors/Metal Deactivators
[0121] Corrosion inhibitors are used to reduce the degradation of
metallic parts that are in contact with the lubricating oil
composition. Suitable corrosion inhibitors include aryl thiazines,
alkyl substituted dimercapto thiodiazoles thiadiazoles and mixtures
thereof. Such additives may be used in an amount of 0.01 to 5 wt %,
preferably 0.01 to 1.5 wt %, more preferably 0.01 to 0.2 wt %,
still more preferably 0.01 to 0.1 wt % (on an as-received basis)
based on the total weight of the lubricating oil composition.
Seal Compatibility Additives
[0122] Seal compatibility agents help to swell elastomeric seals by
causing a chemical reaction in the fluid or physical change in the
elastomer. Suitable seal compatibility agents for lubricating oils
include organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (butylbenzyl phthalate, for example), and polybutenyl
succinic anhydride and sulfolane-type seal swell agents such as
Lubrizol 730-type seal swell additives. Such additives may be used
in an amount of 0.01 to 3 wt %, preferably 0.01 to 2 wt % on an
as-received basis.
Anti-Foam Agents
[0123] Anti-foam agents may advantageously be added to lubricant
compositions. These agents retard the formation of stable foams.
Silicones and organic polymers are typical anti-foam agents. For
example, polysiloxanes, such as silicon oil or polydimethyl
siloxane, provide antifoam properties. Anti-foam agents are
commercially available and may be used in conventional minor
amounts along with other additives such as demulsifiers; usually
the amount of these additives combined is less than 1 percent,
preferably 0.001 to 0.5 wt %, more preferably 0.001 to 0.2 wt %,
still more preferably 0.0001 to 0.15 wt % (on an as-received basis)
based on the total weight of the lubricating oil composition.
Inhibitors and Antirust Additives
[0124] Anti-rust additives (or corrosion inhibitors) are additives
that protect lubricated metal surfaces against chemical attack by
water or other contaminants. One type of anti-rust additive is a
polar compound that wets the metal surface preferentially,
protecting it with a film of oil. Another type of anti-rust
additive absorbs water by incorporating it in a water-in-oil
emulsion so that only the oil touches the surface. Yet another type
of anti-rust additive chemically adheres to the metal to produce a
non-reactive surface. Examples of suitable additives include zinc
dithiophosphates, metal phenolates, basic metal sulfonates, fatty
acids and amines. Such additives may be used in an amount of 0.01
to 5 wt %, preferably 0.01 to 1.5 wt % on an as-received basis.
Antiwear Agents
[0125] Antiwear agents or additives may also be included in the
present disclosure. Non-limiting exemplary antiwear agents include
ZDDP, zinc dithiocarbamates, molybdenum dialkyldithiophosphates,
molybdenum dithiocarbamates, other organo molybdenum-nitrogen
complexes, sulfurized olefins, etc.
[0126] A metal alkylthiophosphate and more particularly a metal
dialkyl dithio phosphate in which the metal constituent is zinc, or
zinc dialkyl dithio phosphate (ZDDP) may be present in the
lubricating oils of the present disclosure. ZDDP can be primary,
secondary or mixtures thereof. ZDDP compounds generally are of the
formula Zn[SP(S)(OR.sup.1)(OR.sup.1)(OR.sup.2)].sub.2 where R.sup.1
and R.sup.2 are C.sub.1-C.sub.18 alkyl groups, preferably
C.sub.2-C.sub.12 alkyl groups. These alkyl groups may be straight
chain or branched and can be derived from primary alcohols,
secondary alcohols and mixtures thereof.
[0127] Preferable zinc dithiophosphates which are commercially
available include secondary zinc dithiophosphates such as those
available from for example, the Lubrizol Corporation under the
trade designations "LZ 677A", "LZ 1095" and "LZ 1371", from for
example Chevron Oronite under the trade designation "OLOA 262" and
from, for example, Afton Chemical under the trade designation
"HITEC 7169".
[0128] The ZDDP is typically used in amounts of from 0.4 wt % to
1.2 wt %, preferably from 0.5 wt % to 1.0 wt %, and more preferably
from 0.6 wt % to 0.8 wt %, based on the total weight of the
lubricating oil, although more or less can often be used
advantageously. Preferably, the ZDDP is a secondary ZDDP and
present in an amount of from 0.6 to 1.0 wt % of the total weight of
the lubricating oil.
[0129] The term "organo molybdenum-nitrogen complexes" embraces the
organo molybdenum-nitrogen complexes described in U.S. Pat. No.
4,889,647. The complexes are reaction products of a fatty oil,
dithanolamine and a molybdenum source. Specific chemical structures
have not been assigned to the complexes. U.S. Pat. No. 4,889,647
reports an infrared spectrum for a typical reaction product of that
disclosure; the spectrum identifies an ester carbonyl band at 1740
cm.sup.-1 and an amide carbonyl band at 1620 cm.sup.-1. The fatty
oils are glyceryl esters of higher fatty acids containing at least
12 carbon atoms up to 22 carbon atoms or more. The molybdenum
source is an oxygen-containing compound such as ammonium
molybdates, molybdenum oxides and mixtures.
[0130] Other organo molybdenum complexes which can be used in the
present disclosure are tri-nuclear molybdenum-sulfur compounds
described in EP 1 040 115 and WO 99/31113 and the molybdenum
complexes described in U.S. Pat. No. 4,978,464.
Friction Modifiers
[0131] A friction modifier is any material or materials that can
alter the coefficient of friction of a surface lubricated by any
lubricant or fluid containing such material(s). Friction modifiers,
also known as friction reducers, or lubricity agents or oiliness
agents, and other such agents that change the ability of base oils,
formulated lubricant compositions, or functional fluids, to modify
the coefficient of friction of a lubricated surface may be
effectively used in combination with the base oils or lubricant
compositions of the present disclosure if desired. Friction
modifiers that lower the coefficient of friction are particularly
advantageous in combination with the base oils and lube
compositions of this disclosure. Friction modifiers may include
metal-containing compounds or materials as well as ashless
compounds or materials, or mixtures thereof. Metal-containing
friction modifiers may include metal salts or metalligand complexes
where the metals may include alkali, alkaline earth, or transition
group metals. Such metal-containing friction modifiers may also
have low-ash characteristics. Transition metals may include Mo, Sb,
Sn, Fe, Cu, Zn, and others. Ligands may include hydrocarbyl
derivative of alcohols, polyols, glycerols, partial ester
glycerols, thiols, carboxylates, carbamates, thiocarbamates,
dithiocarbamates, phosphates, thiophosphates, dithiophosphates,
amides, imides, amines, thiazoles, thiadiazoles, dithiazoles,
diazoles, triazoles, and other polar molecular functional groups
containing effective amounts of O, N, S, or P, individually or in
combination. In particular, Mo-containing compounds can be
particularly effective such as for example Mo-dithiocarbamates,
Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am),
Mo-alcoholates, Mo-alcohol-amides, etc. See U.S. Pat. Nos.
5,824,627, 6,232,276, 6,153,564, 6,143,701, 6,110,878, 5,837,657,
6,010,987, 5,906,968, 6,734,150, 6,730,638, 6,689,725, 6,569,820;
and also WO 99/66013; WO 99/47629: and WO 98/26030.
[0132] Ashless friction modifiers may also include lubricant
materials that contain effective amounts of polar groups, for
example, hydroxyl-containing hydrocarbyl base oils, glycerides,
partial glycerides, glyceride derivatives, and the like. Polar
groups in friction modifiers may include hydrocarbyl groups
containing effective amounts of O, N, S, or P, individually or in
combination. Other friction modifiers that may be particularly
effective include, for example, salts (both ash-containing and
ashless derivatives) of fatty acids, fatty alcohols, fatty amides,
fatty esters, hydroxyl-containing carboxylates, and comparable
synthetic long-chain hydrocarbyl acids, alcohols, amides, esters,
hydroxy carboxylates, and the like. In some instances fatty organic
acids, fatty amines, and sulfurized fatty acids may be used as
suitable friction modifiers.
[0133] Useful concentrations of friction modifiers may range from
0.01 weight percent to 10-15 weight percent or more, often with a
preferred range of 0.1 weight percent to 5 weight percent.
Concentrations of molybdenum-containing materials are often
described in terms of Mo metal concentration. Advantageous
concentrations of Mo may range from 10 ppm to 3000 ppm or more, and
often with a preferred range of 20-2000 ppm, and in some instances
a more preferred range of 30-1000 ppm. Friction modifiers of all
types may be used alone or in mixtures with the materials of this
disclosure. Often mixtures of two or more friction modifiers, or
mixtures of friction modifier(s) with alternate surface active
material(s), are also desirable.
TABLE-US-00002 Typical Amounts of Various Lubricant Oil Components
Approximate wt % Approximate wt % Compound (useful) (preferred)
Friction Modifiers 0.01-15 0.01-5 Antiwear Additives 0.01-6 0.01-4
Detergents 0.01-8 0.01-4 Dispersants 0.1-20 0.1-8 Antioxidants
0.01-5 0.01-1.5 Anti-foam Agents 0.001-1 0.001-0.1 Corrosion
Inhibitors 0.01-5 0.01-1.5 Co-basestocks 0-50 0-40 Base Oils
Balance Balance
Lubricant Composition Properties
[0134] The lubricant compositions including the PAO-PAG block
copolymer fluid described above provide improved emulsion
characteristics, and also improved oxidative stability (PDSC) and
elastomer compatibility (ACEA) in engine oil lubrication
applications. The use of these PAO-PAG block copolymers are
desirable in engine oils in the presence of salicylate, sulfonate
and phenate detergents, along with antioxidants and ashless
antioxidants, along with succinimide based dispersants, along with
zinc dialkyldithiophosphates, along with organic and metallic
friction modifiers, along with corrosion inhibitors, along with
defoamants and in the presence of Group I, Group II, Group III,
Group IV and Group V base oils. The PAO-PAG block copolymer are
useful in all engine oil applications, but are particularly useful
in low viscosity fluids with a kinematic viscosity at 100.degree.
C. between 9 and 13 cSt, more preferred at a kinematic viscosity
range at 100.degree. C. between 5 and 9, and even more preferential
below 5 cSt at 100.degree. C. Furthermore, the use of the PAO-PAG
block copolymers are desirable in engine oils with low sulfated ash
levels (measured by ASTM D874) of 1 wt % or less, more preferred at
levels 0.8 wt % or less.
[0135] In terms of emulsion as measured by as measured by ASTM
D7563, the ability of the engine lubricating oil of this disclosure
contaminated with water and fuel to emulsify water contamination is
improved as compared to the ability of an engine lubricating oil
contaminated with water and fuel to emulsify water contamination
using a lubricating oil containing a minor component other than the
coupled block copolymer.
[0136] In terms of oxidative stability as measured by PDSC,
thermo-oxidative stability is improved as compared to
thermo-oxidative stability achieved using a lubricating oil
containing a minor component other than the coupled block
copolymer.
[0137] In terms of elastomer compatibility as measured by ACEA,
elastomer compatibility is improved as compared elastomer
compatibility achieved using a lubricating oil containing a minor
component other than the coupled block copolymer.
[0138] In the above detailed description, the specific embodiments
of this disclosure have been described in connection with its
preferred embodiments. However, to the extent that the above
description is specific to a particular embodiment or a particular
use of this disclosure, this is intended to be illustrative only
and merely provides a concise description of the exemplary
embodiments. Accordingly, the disclosure is not limited to the
specific embodiments described above, but rather, the disclosure
includes all alternatives, modifications, and equivalents falling
within the true scope of the appended claims. Various modifications
and variations of this disclosure will be obvious to a worker
skilled in the art and it is to be understood that such
modifications and variations are to be included within the purview
of this application and the spirit and scope of the claims.
[0139] The following are examples of the present disclosure and are
not to be construed as limiting.
EXAMPLES
[0140] Lubricating oils were prepared for ASTM D7563 testing. Three
baseline candidates using typical levels of engine oil additives
were used and compared to samples top-treated (1-5 wt %) with
commercial PAGs ("capped PAG") and a synthesized derivative of PAG
("coupled PAG"). The samples are identified in the figures.
[0141] The samples were tested in accordance with ASTM D7563. ASTM
D7563 measures the ability of an oil to emulsify water and E85
fuel. In the Examples, 10 vol % water and 10 vol % fuel were mixed
into the lubricating oil sample and stored for 24 hours at
0.degree. C. at 25.degree. C. Afterwards, the amount of oil, water,
and emulsion was observed and reported. In ASTM D7563, an emulsion
is desirable (i.e., no observable aqueous layer at the bottom of
the container).
[0142] In FIG. 1, two graphs show results of the ASTM D7563 E85
emulsion testing. One test was conducted at 0.degree. C. and the
other test conducted at 25.degree. C. The presence of any amount of
a water phase was a failing result. Comparative examples A, B and C
all showed very poor failing results. The comparative example top
treated with the coupled PAG, at 5 wt %, showed very good passing
emulsion properties, above the commercially available PAGs. The use
of the coupled PAG, in typical engine oil, at 1-3 wt %, more
preferably at 3-5 wt % can reduce the aqueous phase separation from
12-14 vol % to 0 vol %.
[0143] Samples were also tested using Pressure Differential
Scanning Calorimetry (PDSC) at 210.degree. C. and 100 psi air. This
test measures enthalpy change over time. The point at which a
significant exotherm occurs is considered the induction time. A
greater resistance to oxidation induction is desirable. A baseline
candidate was compared to samples top-treated (3-5 wt %) with
commercial PAGs, a coupled PAG and a polyetheramine precursor to
the synthesized PAG. The results are set forth in FIG. 2. The
coupled PAG was the only component top-treat that improved the
oxidation induction time of Comparative Example D.
[0144] Elastomer compatability performance was evaluated for four
Association des Constructucteurs Europeens D'Automobiles (ACEA)
elastomers: Viton, Acrylate, Silicone, and Nitrile. A baseline
candidate (Comparative Example D) was compared to samples
top-treated (1-5 wt %) with commercial PAGs coupled PAGs and a
polyetheramine. The results are shown in FIG. 3. Three component
top-treated samples showed no-harm in ACEA elastomer compatibility
testing. The coupled PAG (Comparative Example D+3 wt % coupled PAG)
provided benefits for Nitrile and Polyacrylate compatibility and
exhibited no harm for Viton and Silicone compatibility.
[0145] All patents and patent applications, test procedures (such
as ASTM methods, UL methods, and the like), and other documents
cited herein are fully incorporated by reference to the extent such
disclosure is not inconsistent with this disclosure and for all
jurisdictions in which such incorporation is permitted.
[0146] When numerical lower limits and numerical upper limits are
listed herein, ranges from any lower limit to any upper limit are
contemplated. While the illustrative embodiments of the disclosure
have been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the disclosure. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present disclosure, including all features
which would be treated as equivalents thereof by those skilled in
the art to which the disclosure pertains.
[0147] The present disclosure has been described above with
reference to numerous embodiments and specific examples. Many
variations will suggest themselves to those skilled in this art in
light of the above detailed description. All such obvious
variations are within the full intended scope of the appended
claims.
* * * * *
References