U.S. patent application number 16/175329 was filed with the patent office on 2019-05-16 for lubricant grease compositions comprising polymeric diphenylamine antioxidants.
The applicant listed for this patent is EXXONMOBIL RESEARCH AND ENGINEERING COMPANY. Invention is credited to Michael L. Alessi, Mary Dery, Liehpao Oscar Famg, Graciela Sanchez Jimenez, David Khoshabo, Paul Odorisio, Bridgett Rakestraw, Sai Shum, Andrew Edmund Taggi, Rebecca Cristine Vieira.
Application Number | 20190144776 16/175329 |
Document ID | / |
Family ID | 66332706 |
Filed Date | 2019-05-16 |
![](/patent/app/20190144776/US20190144776A1-20190516-C00001.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00002.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00003.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00004.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00005.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00006.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00007.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00008.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00009.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00010.png)
![](/patent/app/20190144776/US20190144776A1-20190516-C00011.png)
View All Diagrams
United States Patent
Application |
20190144776 |
Kind Code |
A1 |
Famg; Liehpao Oscar ; et
al. |
May 16, 2019 |
LUBRICANT GREASE COMPOSITIONS COMPRISING POLYMERIC DIPHENYLAMINE
ANTIOXIDANTS
Abstract
Disclosed in certain embodiments is a lubricating grease
composition comprising an antioxidant polymer (e.g., oligomer)
composition comprising repeat units of diphenylamine monomers of
formula I ##STR00001## wherein R is H, C.sub.1-C.sub.18 alkyl,
C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl,
--C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl and R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are each independently H or a linear or
branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl and wherein
the number average molecular weight (Mn) of the polymer composition
is from about 350 g/mol to about 5000 g/mol.
Inventors: |
Famg; Liehpao Oscar;
(Lawrenceville, NJ) ; Jimenez; Graciela Sanchez;
(Puebla, MX) ; Dery; Mary; (Putnam Valley, NY)
; Odorisio; Paul; (Leonia, NJ) ; Rakestraw;
Bridgett; (Brewster, NY) ; Shum; Sai;
(Pleasantville, NY) ; Khoshabo; David; (Bethel,
CT) ; Alessi; Michael L.; (Rose Valley, PA) ;
Vieira; Rebecca Cristine; (Morristown, NJ) ; Taggi;
Andrew Edmund; (New Hope, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EXXONMOBIL RESEARCH AND ENGINEERING COMPANY |
Annandale |
NJ |
US |
|
|
Family ID: |
66332706 |
Appl. No.: |
16/175329 |
Filed: |
October 30, 2018 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62579643 |
Oct 31, 2017 |
|
|
|
Current U.S.
Class: |
508/563 |
Current CPC
Class: |
C10N 2050/10 20130101;
C10M 2201/006 20130101; C10M 2201/1036 20130101; C10N 2020/02
20130101; C10M 169/00 20130101; C10M 2217/0456 20130101; C10M
2219/0445 20130101; C10M 2207/1265 20130101; C10N 2030/04 20130101;
C10M 149/14 20130101; C10N 2030/10 20130101; C10M 2217/041
20130101; C10M 2217/046 20130101; C10N 2020/04 20130101; C10N
2040/02 20130101; C10N 2010/06 20130101; C10M 2205/0206 20130101;
C10M 2207/1256 20130101; C10N 2030/02 20130101; C10N 2010/02
20130101; C10N 2010/04 20130101 |
International
Class: |
C10M 169/00 20060101
C10M169/00 |
Claims
1. A lubricating grease composition comprising a base oil; a
thickener; and from about 0.01 wt % to about 20 wt %, based on the
total weight of the lubricating grease composition, of an
antioxidant polymer composition comprising repeat units of
diphenylamine monomers of formula I ##STR00013## wherein R is H,
C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18
alkynyl, --C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl and R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are each independently H or a linear
or branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl and wherein
the number average molecular weight (Mn) of the polymer composition
is from about 350 g/mol to about 5000 g/mol.
2. The lubricating grease composition according to claim 1, wherein
the thickener is selected from the group consisting of simple
lithium soap, lithium complex soap, polyurea, calcium sulfonate,
aluminum soap, calcium soap, mixed aluminum/calcium, clay, polymer
and a combination thereof.
3. The lubricating grease composition according to claim 2, wherein
the thickener comprises a lithium complex soap.
4. The lubricating grease composition according to claim 1,
comprising one or more components selected from the group
consisting of other antioxidants, antiwear additives, polymers,
detergents, dispersants, pour point depressants, corrosion
inhibitors, metal deactivators, complexing agents, antifoam agents,
inhibitors, antirust additives, and friction modifiers.
5. The grease composition of claim 1, wherein the base oil
comprises at least one of a Group I oil, a Group II oil, a Group
III oil, a Group IV oil, a Group V oil, a gas-to-liquid oil, or
combinations thereof.
6. The lubricating grease composition according to claim 1, having
an ISO Viscosity grades of about 100 to about 680.
7. The lubricating grease composition according to claim 1, having
an NLGI consistency grade of 000 to 6.
8. The lubricating grease composition according to claim 1, wherein
the Mn of the antioxidant antioxidant polymer composition is from
about 400 g/mol to about 5000 g/mol.
9. The lubricating grease composition according to claim 1, wherein
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently H or a
linear or branched C.sub.4-C.sub.10 alkyl.
10. The lubricating grease composition according to claim 1,
wherein R is H.
11. The lubricating grease composition of claim 1, wherein the
antioxidant polymer composition is an oligomer composition.
12. A lubricating grease composition comprising a base oil; a water
insoluble thickener; and from about 0.01 wt % to about 20 wt %,
based on the total weight of the lubricating grease composition, of
a polymer composition comprising repeat units of diphenylamine
monomers of formula I ##STR00014## wherein R is H, C.sub.1-C.sub.18
alkyl, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl,
--C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl and R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are each independently H or a linear or
branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl, and wherein
the polymer composition comprises .ltoreq.70 wt % residual monomers
of formula I.
13. A lubricating grease composition comprising a base oil; and
from about 0.01 wt % to about 20 wt %, based on the total weight of
the lubricating grease composition, of an antioxidant polymer
composition comprising repeat units of diphenylamine monomers of
formula I ##STR00015## wherein R is H, C.sub.1-C.sub.18 alkyl,
C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl,
--C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl and R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are each independently H or a linear or
branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl and wherein
the number average molecular weight (Mn) of the polymer composition
is from about 350 g/mol to about 5000 g/mol.
14. A method of improving the high temperature performance of a
bearing comprising adding to the bearing the lubricating grease
composition of claim 1.
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 62/579,643, filed on Oct. 31, 2017, which is herein
incorporated by reference in its entirety.
FIELD
[0002] This disclosure relates to grease compositions with improved
high temperature bearing performance. In particular, this
disclosure relates to greases, methods for improving high
temperature performance of a lubricating grease in a bearing or
other mechanical component lubricated with the lubricating grease
and methods of making and using the same.
BACKGROUND
[0003] Lubricant oxidative stability is one of the key parameters
controlling oil life, which translates to oil drain interval in
practical terms. Additionally, deposit formation is an issue
associated with the decomposition of the base stock molecules
mostly propagated by oxidative chain reactions. There are several
conventional approaches to improve the resistance to oxidation of a
finished lubricant product, but most products are formulated using
small molecules such as diphenylamine (DPA) or a phenolic
antioxidant.
[0004] Improved oxidation stability is necessary to increase oil
life and oil drain intervals, thus reducing the amount of used oil
generated as a consequence of more frequent oil changes. Longer oil
life and oil drain intervals are key benefits that are desirable to
end customers. Traditional antioxidant packages provide standard
protection leaving the main differentiation hinging on the quality
of the base stock in the formulation.
[0005] What is needed are newly designed lubricants capable of
controlling oxidation and oil thickening for longer periods of time
as compared to conventional lubricants. Further, what are needed
are newly designed lubricants that enable extended oil life in
combination with desired deposit control and cleanliness
performance.
[0006] Lubricating formulations and greases with a wide assortment
of different materials are known. For example, lithium complex
greases are well known and can be made from any of a wide variety
of base stocks of lubricating oil viscosity, as well as mixtures of
base stocks. For example, lithium complex greases that comprise a
lithium complex thickener and a lubricating base oil are well
known. Greases have varied levels of desirable grease
characteristics, such as dropping point, penetration, mechanical
stability, shear stability, oxidation resistance, high temperature
resistance, etc., based on its composition, which may include the
use of polymers. The above characteristics are used to describe the
lubricating life of a particular grease.
[0007] The use of polymers to impart desirable properties to grease
is known and widely practiced by grease manufacturers; see, for
example, the description of various thickeners in Manufacture and
Application of Lubricating Greases (1954), Reinhold, N.Y. 1954 and
Alteration of Grease Characteristics with New Generation Polymers,
G. D. Hussey, NLGI Spokesman, August 1987. Oil soluble polymers
have been used, for example, to increase the structural stability
of greases and to confer reduced oil separation, and increased
water resistance. Although these benefits could be obtained without
polymers by using lubricating oils having high viscosity base
stocks, the resulting debit on low temperature mobility (i.e.,
pumpability) severely limits a non-polymer approach.
[0008] Currently, lithium soap based greases represent
approximately 80% of the lubricating grease market and generally
provide acceptable lubricating performance. However, lithium soap
based greases are limited by their resistance to high-temperatures,
wet environments, and shear. For example, lithium soap based grease
in polyalphaolefin (PAO) based fluid maxes out at 140.degree. C.
Currently available high-temperature lithium greases are either
composed of solid particles, such as polytetrafluoroethylene
(PTFE), which induce wear and tear on the lubricated surface(s)
(such as bearings, gears, slide plates, etc.), or polyester (POE)
base oils, which are costly, are limited in certain properties and
impractical for manufacture.
[0009] Polymer additives are well established for enhancing grease
performance at low treatment levels as reported in NLGI Paper
Benefits of Polymer Additives in Grease, Larson, et al., NLGI
Spokesman, ISSN: 00276782, Vol: 73, Issue 7. As discussed in
Larson, the challenges facing grease manufacturers face can be
addressed with the inclusion of polymer additives in a variety of
grease types. The benefits of polymer additives in Larson are shown
to include improved shear stability, enhanced water resistance, and
increased yield. In addition to performance enhancements, selected
polymer additives may provide economic benefits through increased
grease yields of up to 17%.
[0010] Polymers that have been studied as grease additives include
polyisobutylene (PIB), ethylene-propylene copolymers (OCP),
styrene-hydrogenated butadiene (SBR), styrene-hydrogenated isoprene
(SI), radial hydrogenated polyisoprene (star), acid functionalized
polymers (FP), polymethacrylate (PMA), styrene ester copolymers
(SE), and styrene ethylene butylene copolymers (SEBCP). These
polymers have been used as co-thickeners e.g. with a calcium soap
as described in U.S. Pat. No. 5,084,193 (Waynick) or as the sole
thickener as in U.S. Pat. No. 5,874,391 (Meijer).
[0011] As technology advances and throughput increases with
mechanical devices, there is an increased demand for higher
temperature operating conditions and lubricating compositions, such
as grease The working life of grease is limited in such an
environment, which results in greater wear on the equipment and
longer downtimes as a result of maintenance (e.g., re-greasing the
ball bearings and replacement/maintenance of warn parts of the
equipment).
[0012] Thus, a need exists for lubricating greases that have
enhanced/extended high temperature resistance.
SUMMARY
[0013] In certain embodiments, the present disclosure is directed
to a lubricating grease composition comprising a base oil, water
insoluble thickener and an antioxidant polymer (e.g., oligomer)
composition comprising repeat units of diphenylamine monomers of
formula I
##STR00002##
wherein R is H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl, --C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl
and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently H
or a linear or branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18
alkoxy, C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl. In certain
embodiments, the number average molecular weight (Mn) of the
antioxidant polymer (e.g., oligomer) composition is at least about
350 g/mol or from about 350 g/mol to about 5000 g/mol.
[0014] Also disclosed in certain embodiments is a lubricating oil
composition comprising an antioxidant polymer (e.g., oligomer)
composition comprising .ltoreq.about 99 wt %, .ltoreq.about 90 wt
%, .ltoreq.about 80 wt %, .ltoreq.about 70 wt %, .ltoreq.about 65
wt %, .ltoreq.about 60 wt %, .ltoreq.about 55 wt %, .ltoreq.about
50 wt %, .ltoreq.about 45 wt %, .ltoreq.about 40 wt %,
.ltoreq.about 35 wt %, .ltoreq.about 30 wt %, .ltoreq.about 25 wt
%, .ltoreq.about 20 wt %, .ltoreq.about 15 wt %, .ltoreq.about 10
wt %, .ltoreq.about 5 wt %, .ltoreq.about 1 wt %, .ltoreq.about 0.5
wt %, .ltoreq.about 0.1 wt %, .ltoreq.about 0.05 wt % or
.ltoreq.about 0.01 wt % residual monomers of formula I. For
example, in certain embodiments, disclosed is an antioxidant
polymer (e.g., oligomer) composition comprising repeat units of
diphenylamine monomers of formula I, wherein the composition
comprises from any one of about 0.01 wt %, about 0.05 wt %, about
0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %,
about 4 wt %, about 5 wt %, about 7 wt %, about 9 wt %, ab about 70
wt % out 11 wt % or about 13 wt % to any one of about 15 wt %,
about 18 wt %, about 21 wt %, about 24 wt %, about 27 about 70 wt %
wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %,
about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about
70 wt %, about 80 wt % or about 99 wt % residual monomers of
formula I, based on the total weight of the antioxidant
composition.
[0015] In certain embodiments wherein the antioxidant polymer
(e.g., oligomer) composition comprises residual monomers, about 90
wt %, about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt % or
about 95 wt % to about 96 wt %, about 97 wt %, about 98 wt %, about
99 wt % or 100 wt % of the residual monomer(s) is of formula I
wherein one or both of R.sub.1 and R.sub.4 are independently
C.sub.4-C.sub.18 alkyl, C.sub.4-C.sub.18 alkenyl or
C.sub.7-C.sub.21 aralkyl, based on the total weight of residual
monomer(s).
[0016] Also disclosed are lubricating grease compositions
comprising a base oil, water insoluble thickener and an antioxidant
polymer (e.g., oligomer) composition comprising repeat units of
diphenylamine monomers of formula I. The grease composition can be
used in many industrial and consumer applications such as
lubricating a bearing such as a rolling element bearing, e g. a
spherical roller bearing, a taper roller bearing, a cylindrical
roller bearing, a needle roller bearing, a ball bearing, and may
also be used to lubricate a sliding or plain bearing. The grease
composition can also be used in coupling and gearing
applications.
DETAILED DESCRIPTION
[0017] In certain embodiments, the present disclosure is directed
to a lubricating grease composition comprising a base oil, water
insoluble thickener and an antioxidant polymer (e.g., oligomer)
composition comprising repeat units of diphenylamine monomers of
formula I
##STR00003##
[0018] wherein R is H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl, C.sub.2-C.sub.18 alkynyl, --C(O)C.sub.1-C.sub.18 alkyl,
--C(O)aryl; and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each
independently H or a linear or branched C.sub.1-C.sub.18 alkyl,
C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkylamino,
C.sub.1-C.sub.18 dialkylamino, C.sub.1-C.sub.18 alkylthio,
C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl or
C.sub.7-C.sub.21 aralkyl. In certain embodiments, the number
average molecular weight (Mn) of the antioxidant polymer (e.g.,
oligomer) composition is at least about 350 g/mol or from about 350
g/mol to about 5000 g/mol.
[0019] In other embodiments, the antioxidant polymer (e.g.,
oligomer) compositions of the disclosure have an Mn of from about
900 g/mol or about 1000 g/mol to about 1200 g/mol or an Mn of any
one of from about 400 g/mol, about 430 g/mol, about 460 g/mol,
about 490 g/mol, about 520 g/mol, about 550 g/mol, about 580 g/mol,
about 610 g/mol, about 640 g/mol, about 670 g/mol, about 700 g/mol
or about 730 g/mol g/mol to any one of about 760 g/mol, about 790
g/mol, about 820 g/mol, about 850 g/mol, about 880 g/mol, about 910
g/mol, about 940 g/mol, about 970 g/mol, about 1000 g/mol, about
1030 g/mol, about 1060 g/mol, about 1090 g/mol, about 1120 g/mol,
about 1150 g/mol, about 1180 g/mol, about 1210 g/mol, about 1240
g/mol, about 1270 g/mol, about 1300 g/mol, about 1400 g/mol, about
1500 g/mol, about 1600 g/mol, about 1700 g/mol, about 2000 g/mol,
about 2100 g/mol, about 2200 g/mol, about 2300 g/mol, about 2400
g/mol, about 2500 g/mol, about 3000 g/mol, about 3500 g/mol, about
4000 g/mol or about 5000 g/mol.
[0020] The number average molecular weight can be determined, for
example, by gel permeation chromatography (GPC) techniques with a
polystyrene standard. GPC conditions may include testing relative
to a set of polystyrene standards (EasiCal PS-1, low and high and
PS162). Samples are prepared in tetrahydrofuran (THF) and duplicate
injections of solutions are run. Similar conditions may also be
employed.
[0021] In certain embodiments, less than about 25 percent by weight
of the antioxidant composition contains molecules having a
molecular weight of less than about 1000 g/mol.
[0022] In certain embodiments, the present disclosure is directed
to a lubricating grease composition comprising a base oil, water
insoluble thickener and an antioxidant polymer (e.g., oligomer)
composition comprising repeat units of diphenylamine monomers of
formula II
##STR00004##
wherein R and R' are each independently H or a linear or branched
C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl or
C.sub.7-C.sub.21 aralkyl. In certain embodiments, R and R' are each
independently H, tert-butyl or tert-octyl.
[0023] Linear or branched alkyl includes methyl, ethyl, propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl,
n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and
octadecyl. Alkyl groups mentioned herein are linear or
branched.
[0024] The alkyl portion of alkoxy, alkylamine, dialkylamino and
alkylthio groups are linear or branched and include the alkyl
groups mentioned above.
[0025] Alkenyl is an unsaturated alkyl, for instance allyl. Alkynyl
includes a triple bond.
[0026] Aralkyl includes benzyl, .alpha.-methylbenzyl,
.alpha.,.alpha.-dimethylbenzyl and 2-phenylethyl.
[0027] Diphenylamine antioxidants are commercially available, for
example under the trade names IRGANOX L57, IRGANOX L67 and IRGANOX
L01.
[0028] In certain embodiments, the antioxidant polymer (e.g.,
oligomer) compositions of the disclosure can be prepared by a
process comprising subjecting diphenylamine monomers of formula
I
##STR00005##
wherein R is H, C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl, --C(O)C.sub.1-C.sub.18 alkyl, --C(O)aryl;
and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently H
or a linear or branched C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18
alkoxy, C.sub.1-C.sub.18 alkylamino, C.sub.1-C.sub.18 dialkylamino,
C.sub.1-C.sub.18 alkylthio, C.sub.2-C.sub.18 alkenyl,
C.sub.2-C.sub.18 alkynyl or C.sub.7-C.sub.21 aralkyl to
dehydrocondensation conditions.
[0029] Dehydrocondensation conditions comprise exposing monomers of
formula I to oxidative conditions, for example, by exposure to a
compound capable of forming free radicals. Compounds capable of
forming free radicals include inorganic and organic peroxides, such
as di-t-butylperoxide and di-t-amylperoxide. The
dehydrocondensation reaction may be performed neat, that is,
without added solvent, or may be performed in the presence of a
solvent. Suitable solvents include alkanes such as hexane, heptane,
octane, nonane, decane, undecane or dodecane. Dehydrocondensation
may be performed in the presence of a base stock (e.g., ester,
mineral, synthetic, GTL or alkyl naphthalene base stocks).
[0030] In some embodiments, the dehydrocondensation conditions
comprise reaction temperatures of any one of from about 40.degree.
C., about 60.degree. C., about 80.degree. C., about 100.degree. C.,
about 120.degree. C., about 140.degree. C. or about 160.degree. C.
to any one of about 180.degree. C., about 200.degree. C., about
220.degree. C., about 240.degree. C. or about 250.degree. C.
[0031] In certain embodiments, the dehydrocondensation conditions
comprise a reaction time of any one of from about 0.3 hours, about
0.5 hour, about 1 hour, about 2 hours, about 3 hours, about 4
hours, about 5 hours or about 6 hours to any one of about 7 hours,
about 8 hours, about 9 hours, about 10 hours, about 11 hours or
about 12 hours. In other embodiments, the dehydrocondensation
conditions may comprise a reaction time of from any one of about 12
hours, about 24 hours, about 36 hours, about 48 hours or about 60
hours to any one of about 72 hours, about 84 hours, about 96 hours,
about 108 hours or about 120 hours.
[0032] The oxidative conditions remove hydrogen from the monomers,
which subsequently couple through C--N, C--C or N--N bonds. When an
alkane solvent is used, the solvent appears to be inert and to not
be involved in the reaction. Therefore, the produced antioxidant
polymer (e.g., oligomer) may contain no alkane solvent
fragments.
[0033] The term "oligomer comprising repeat units of diphenylamine
monomers" means the oligomers contain "reacted in" monomers, that
is, radicals of monomers.
[0034] The antioxidant polymer (e.g., oligomer) compositions of the
present disclosure may contain a mixture of different chain
lengths. For example, the composition may contain residual
unreacted monomer as well as fragments or chains having molecular
weights above or below the ranges mentioned above. Residual monomer
means unreacted monomer. The antioxidant polymer (e.g., oligomer)
may be purified, for example by a step comprising chromatography or
distillation. In one embodiment, the produced antioxidant polymer
(e.g., oligomer) composition may be subject to reduced pressure to
remove residual monomer.
[0035] Accordingly, the antioxidant polymer (e.g., oligomer)
composition of the present disclosure may contain .ltoreq.about 99
wt %, .ltoreq.about 90 wt %, .ltoreq.about 80 wt %, .ltoreq.about
70 wt %, .ltoreq.about 65 wt %, .ltoreq.about 60 wt %,
.ltoreq.about 55 wt %, .ltoreq.about 50 wt %, .ltoreq.about 45 wt
%, .ltoreq.about 40 wt %, .ltoreq.about 35 wt %, .ltoreq.about 30
wt %, .ltoreq.about 25 wt %, .ltoreq.about 20 wt %, .ltoreq.about
15 wt %, .ltoreq.about 10 wt % .ltoreq.about 5 wt %, .ltoreq.about
1 wt %, .ltoreq.about 0.5 wt %, .ltoreq.about 0.1 wt %,
.ltoreq.about 0.05 wt % or .ltoreq.about 0.01 wt % residual
monomers of formula I, based on the weight of the composition. For
example, in certain embodiments, disclosed is an antioxidant
polymer (e.g., oligomer) composition comprising repeat units of
diphenylamine monomers of formula I, wherein the composition
comprises from any one of about 0.01 wt %, about 0.05 wt %, about
0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %,
about 4 wt %, about 5 wt %, about 7 wt %, about 9 wt %, about 11 wt
% or about 13 wt % to any one of about 15 wt %, about 18 wt %,
about 21 wt %, about 24 wt %, about 27 wt %, about 30 wt %, about
35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt
%, about 60 wt %, about 65 wt % about 70 wt %, about 80 wt % or
about 99 wt % residual monomers of formula I, based on the total
weight of the antioxidant composition.
[0036] In certain embodiments, the purification steps to remove
residual monomers include subjecting the antioxidant polymer (e.g.,
oligomer) composition to reduced pressure. In certain embodiments,
the remaining monomer in the composition will include higher
molecular weight monomers, e.g., di- or tri-alkyl substituted
monomers. In some embodiments, wherein the antioxidant polymer
(e.g., oligomer) composition contains residual monomer, any one of
from about 90 wt %, about 91 wt %, about 92 wt %, about 93 wt %,
about 94 wt % or about 95 wt % to any one of about 96 wt %, about
97, about 98, about 99 or 100 wt % of the residual monomer is of
formula I wherein R.sub.1 and R.sub.4 are independently
C.sub.4-C.sub.18 alkyl, C.sub.4-C.sub.18 alkenyl or
C.sub.7-C.sub.21 aralkyl, based on the total weight of residual
monomer.
[0037] In certain embodiments, the antioxidant polymer (e.g.,
oligomer) composition may also be characterized by its viscosity.
For example, the present antioxidant polymer (e.g., oligomer)
compositions of the disclosure may have a kinematic viscosity at
100.degree. C. of from any one of about 10 cSt to about 2,500 cSt.
In other embodiments, the kinematic viscosity at 100.degree. C. may
be from any one of about 10 cSt, about 20 cSt, about 30 cSt, about
40 cSt, about 50 cSt, about 60 cSt, about 70 cSt, about 80 cSt,
about 81 cSt, about 82 cSt, about 83 cSt, about 84 cSt, about 85
cSt, about 86 cSt, about 87 cSt, about 88 cSt, about 89 cSt, about
90 cSt, about 91 cSt, about 92 cSt, about 93 cSt, about 94 cSt,
about 95 cSt, about 96 cSt, about 97 cSt, about 98 cSt or about 99
cSt to any one of about 100 cSt, about 101 cSt, about 102 cSt,
about 103 cSt, about 104 cSt, about 105 cSt, about 106 cSt, about
107 cSt, about 108 cSt, about 109 cSt, about 110 cSt, about 111
cSt, about 112 cSt, about 113 cSt, about 114 cSt, about 115 cSt,
about 116 cSt, about 117 cSt, about 118 cSt, about 119 cSt, about
120 cSt, about 500 cSt, about 1,000 cSt, about 1,500 cSt, about
2,000 cSt or about 2,500 cSt.
[0038] In certain other embodiments of the disclosure, the
antioxidant polymer (e.g., oligomer) compositions may have a
kinematic viscosity 100.degree. C. of from any one of about 120
cSt, about 140 cSt, about 170 cSt, about 190 cSt, about 210 cSt,
about 230 cSt, about 260 cSt, about 310 cSt or about 360 cSt to any
one of about 400 cSt, about 420 cSt, about 450 cSt, about 470 cSt,
about 500 cSt, about 530 cSt, about 570 cSt or about 600 cSt. In
certain other embodiments, the antioxidant polymer (e.g., oligomer)
compositions may be solids.
[0039] Viscosity may be determined according to ASTM D445 or
equivalent or similar methods measured at 100.degree. C.
[0040] In certain embodiments, further monomers may be included in
the polymerization reaction. For example, present antioxidant
polymer (e.g., oligomer)s may contain one or more monomers selected
from the group consisting of other diphenylamines, phenothiazines,
phenoxazines, aminodiphenylamines, methylenedianiline,
toluenediamine, aminophenols, alkylphenols, thiophenols,
phenylenediamines, quinolines, phenyl pyridinediamines,
pyridinepyrimidinediamines, naphthylphenylamines and
phenylpyrimidinediamines.
[0041] In some embodiments, present antioxidant polymer (e.g.,
oligomer) compositions comprise any one of from about 1 mol %, 10
mol %, about 20 mol %, about 30 mol %, about 40 mol % or about 50
mol % to any one of about 60 mol %, about 70 mol %, about 80 mol %,
about 90 mol %, about 95 mol %, about 96 mol %, about 97 mol %,
about 98 mol %, about 99 mol % or 100 mol % diphenylamine monomers
of formula I.
[0042] In certain embodiments, the polymeric compositions disclosed
herein are oligomeric compositions (i.e., dimers, trimers and
tetramers).
[0043] In certain embodiments, the polymeric compositions disclosed
herein comprise one or more of dimers, trimers, tetramers or higher
repeating units (i.e. a antioxidant polymer of 5 or more
monomers).
[0044] In certain embodiments, the polymeric compositions have an
amount of dimers that are greater than the amount of higher
repeating units.
[0045] In certain embodiments, the polymeric compositions have an
amount of trimers that are greater than the amount of higher
repeating units.
[0046] In certain embodiments, the polymeric compositions have a
combined amount of dimers and trimers that are greater than the
amount of higher repeating units.
[0047] In certain embodiments, the polymeric compositions have at
least 75% Mn of greater than 1000. In other embodiments, the
polymeric compositions have about 20% to about 80%, about 25% to
about 75%, about 30% to about 70% or about 40% to about 60% Mn of
greater than 1000.
[0048] In certain embodiments, the polymeric compositions have at
least 75% Mn of less than 1000. In other embodiments, the polymeric
compositions have about 10% to about 100%, about 20% to about 80%,
about 25% to about 75%, about 30% to about 70% or about 40% to
about 60% Mn of less than 1000.
[0049] In certain embodiments, the polymeric compositions have an
amount of dimers of from any one of about 5%, about 10%, about 15%,
about 20%, about 25% or about 30% to any one of about 40%, about
45%, about 50%, about 55%, about 60%, about 70%, about 80%, about
90% or about 100%. In certain embodiments, the dimers have a number
average molecular weight (Mn) of about 300 to about 850.
[0050] In certain embodiments, the polymeric compositions have an
amount of trimers of from any one of about 10%, about 15%, about
20%, about 25%, about 30% or about 40% to any one of about 50%,
about 55%, about 60%, about 65%, about 70%, about 80%, about 90% or
about 100%. In certain embodiments, the trimers have a number
average molecular weight (Mn) of about 400 to about 1200.
[0051] In certain embodiments, the polymeric compositions have an
amount of tetramers of from any one of about 15%, about 20%, about
25%, about 30%, about 40% or about 50% to any one of about 55%,
about 60%, about 65%, about 70%, about 75%, about 80%, about 90% or
about 100%. In certain embodiments, the tetramers have a number
average molecular weight (Mn) of about 500 to about 1500.
[0052] In certain embodiments, the polymeric compositions have an
amount of higher repeating units of from any one of about 5%, about
10%, about 25%, about 30%, about 40% to any one of about 50%, about
60%, about 70%, about 80%, about 90% or about 100%. In certain
embodiments, the higher repeating units have a number average
molecular weight (Mn) of greater than about 1000 or greater than
about 1174.
[0053] In certain embodiments polymeric composition have m/z ions
ranging from 300 to 1000. In certain embodiments, the above m/z
ions include 838 Daltons, 894 Daltons or 911 Daltons.
[0054] In certain embodiments, the polymeric compositions have an
m/z ion count from about 300 to about 1,000 of greater than about
50, greater than about 75, greater than about 100, greater than
about 150, greater than about 200, greater than about 250, greater
than about 300 or greater than about 350. In certain embodiments,
the polymeric compositions have an m/z ion count from about 800 to
about 1,000 of from any one of about 50, about 75, about 100 or
about 150 to any one of about 200, about 250, about 300 or about
350.
[0055] In certain embodiments, the polymeric compositions exhibit a
VIT(h) of greater than about 600, greater than about 650, greater
than about 700, or greater than about 850. In certain embodiments,
the polymeric compositions exhibit a VIT(h) of from any one of
about 600, about 650, or about 700 to any one of about 900, about
1,200 or about 1,500. A comparator monomer composition provides a
VIT(h) of 472. The VIT test is performed by placing a sample of
formulated oil in a glass tube with a homogeneous catalyst
consisting of iron, copper and lead. Air is bubbled through the
sample at a rate of 8 L/h and heated to 150.degree. C. The
kinematic viscosity (KV40) is monitored throughout the test, and
the data fit to a power curve to calculate the time, in hours, it
takes for the sample to reach 150% of its original KV40.
[0056] In certain embodiments, disclosed is a grease formulation
that provides a value of greater than 100, greater than 110 or
greater than 120 when tested according to DIN 51821 FE9 A/1500/6000
@ 140 C (B50, hours) when the grease formulation comprises 1% of
the disclosed antioxidant polymer composition.
[0057] The water insoluble thickener, as discussed below, may
comprise at least one of an aluminum soap, a barium soap, a calcium
soap, a lithium soap, an aluminum salt/soap complex, a barium
salt/soap complex, a calcium salt/soap complex, a lithium salt/soap
complex, or a combination thereof. In certain embodiments, the
water insoluble thickener comprises lithium soap or a lithium
salt/soap complex. In a particular embodiment, the water insoluble
thickener comprises an inorganic clay thickener.
[0058] A wide range of lubricating base oils is known in the art.
Lubricating base oils that may be useful in the present disclosure
are both natural oils, and synthetic oils, and unconventional 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 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.
[0059] Groups I, II, III, IV and V are broad base oil stock
categories 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 have a viscosity index
of from 80 to 120 and contain greater than 0.03% sulfur and/or less
than 90% saturates. Group II base stocks have a viscosity index of
from 80 to 120, and contain less than or equal to 0.03% sulfur and
greater than or equal to 90% saturates. Group III stocks have a
viscosity index greater than 120 and contain less than or equal to
0.03% sulfur and greater than 90% saturates. Group IV includes
polyalphaolefins (PAO). Group V base stock includes base stocks not
included in Groups I-IV. The table below summarizes properties of
each of these five groups.
TABLE-US-00001 saturates sulfur viscosity index Group I <90
and/or >0.03% and .gtoreq.80 and <120 Group II .gtoreq.90 and
.ltoreq.0.03% and .gtoreq.80 and <120 Group III .gtoreq.90 and
.ltoreq.0.03% and .gtoreq.120 Group IV -polyalphaolefins (PAO)-
Group V -all other base stocks not of Groups I-IV-
[0060] 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. 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.
[0061] Group II and/or Group III hydroprocessed or hydrocracked
base stocks, including synthetic oils such as polyalphaolefins,
alkyl aromatics and synthetic esters are also well known base stock
oils.
[0062] Synthetic oils include hydrocarbon oil. Hydrocarbon oils
include oils 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 are 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 olefins or
mixtures thereof may be utilized. See U.S. Pat. Nos. 4,956,122;
4,827,064; and 4,827,073.
[0063] The number average molecular weights of the PAOs, which are
known materials and generally available on a major commercial scale
from suppliers such as ExxonMobil Chemical Company, Chevron
Phillips Chemical Company, BP, and others, typically vary from 250
to 3,000, although PAO's may be made in viscosities up to 100 cSt
(100.degree. C.). The PAOs are typically comprised of relatively
low molecular weight hydrogenated polymers or oligomers of
alphaolefins which include, but are not limited to, C.sub.2 to
C.sub.32 alphaolefins with the C.sub.8 to C.sub.16 alphaolefins,
such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like,
being preferred. The preferred polyalphaolefins are poly-1-hexene,
poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures
thereof and mixed olefin-derived polyolefins. However, the dimers
of higher olefins in the range of C.sub.14 to C.sub.18 may be used
to provide low viscosity base stocks of acceptably low volatility.
Depending on the viscosity grade and the starting polymer (e.g.,
oligomer), the PAOs may be predominantly trimers and tetramers of
the starting olefins, with minor amounts of the higher polymers,
having a viscosity range of 1.5 to 12 cSt. PAO fluids of particular
use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations
thereof. Bi-modal mixtures of PAO fluids having a viscosity range
of 1.5 to about 100 cSt or to about 300 cSt may be used if
desired.
[0064] The PAO fluids may be conveniently made by the
polymerization of an alphaolefin in the presence of a
polymerization catalyst such as the Friedel-Crafts catalysts
including, for example, aluminum trichloride, boron trifluoride or
complexes of boron trifluoride with water, alcohols such as
ethanol, propanol or butanol, carboxylic acids or esters such as
ethyl acetate or ethyl propionate. For example the methods
disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 may be
conveniently used herein. Other descriptions of PAO synthesis are
found in the following U.S. Pat. Nos. 3,742,082; 3,769,363;
3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355;
4,956,122; and 5,068,487. The dimers of the C.sub.14 to C.sub.18
olefins are described in U.S. Pat. No. 4,218,330.
[0065] Other useful lubricant oil base stocks include wax isomerate
base stocks and base oils, comprising hydroisomerized waxy stocks
(e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker
bottoms, etc.), hydroisomerized Fischer-Tropsch waxes,
Gas-to-Liquids (GTL) base stocks and base oils, and other wax
isomerate hydroisomerized base stocks and base oils, or mixtures
thereof Fischer-Tropsch waxes, the high boiling point residues of
Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with
very low sulfur content. The hydroprocessing used for the
production of such base stocks may use an amorphous
hydrocracking/hydroisomerization catalyst, such as one of the
specialized lube hydrocracking (LHDC) catalysts or a crystalline
hydrocracking/hydroisomerization catalyst, preferably a zeolitic
catalyst. For example, one useful catalyst is ZSM-48 as described
in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated
herein by reference in its entirety. Processes for making
hydrocracked/hydroisomerized distillates and
hydrocracked/hydroisomerized waxes are described, for example, in
U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as
well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and
1,390,359. Each of the aforementioned patents is incorporated
herein in their entirety. Particularly favorable processes are
described in European Patent Application Nos. 464546 and 464547,
also incorporated herein by reference. Processes using
Fischer-Tropsch wax feeds are described in U.S. Pat. Nos. 4,594,172
and 4,943,672, the disclosures of which are incorporated herein by
reference in their entirety.
[0066] Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived
base oils, and other wax-derived hydroisomerized (wax isomerate)
base oils be advantageously used in the instant disclosure, and may
have useful kinematic viscosities at 100.degree. C. of 3 cSt to 50
cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt,
as exemplified by GTL 4 with kinematic viscosity of 4.0 cSt at
100.degree. C. and a viscosity index of 141. These Gas-to-Liquids
(GTL) base oils, Fischer-Tropsch wax derived base oils, and other
wax-derived hydroisomerized base oils may have useful pour points
of -20.degree. C. or lower, and under some conditions may have
advantageous pour points of -25.degree. C. or lower, with useful
pour points of -30.degree. C. to -40.degree. C. or lower. Useful
compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax
derived base oils, and wax-derived hydroisomerized base oils are
recited in U.S. Pat. Nos. 6,080,301; 6,090,989, and 6,165,949 for
example, and are incorporated herein in their entirety by
reference.
[0067] The hydrocarbyl aromatics can be used as base oil or base
oil component and can be any hydrocarbyl molecule that contains at
least 5% of its weight derived from an aromatic moiety such as a
benzenoid moiety or naphthenoid moiety, or their derivatives. These
hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes,
alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides,
alkylated bis-phenol A, alkylated thiodiphenol, and the like. The
aromatic can be mono-alkylated, dialkylated, polyalkylated, and the
like. The aromatic can be mono- or poly-functionalized. The
hydrocarbyl groups can also be comprised of mixtures of alkyl
groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl
groups and other related hydrocarbyl groups. The hydrocarbyl groups
can range from C.sub.6 up to C.sub.60 with a range of C.sub.8 to
C.sub.20 often being preferred. A mixture of hydrocarbyl groups is
often preferred, and up to three such substituents may be
present.
[0068] The hydrocarbyl group can optionally contain sulfur, oxygen,
and/or nitrogen containing substituents. The aromatic group can
also be derived from natural (petroleum) sources, provided at least
5% of the molecule is comprised of an above-type aromatic moiety.
Viscosities at 100.degree. C. of about 3 cSt to about 50 cSt are
preferred, with viscosities of about 3.4 cSt to about 20 cSt often
being more preferred for the hydrocarbyl aromatic component. In one
embodiment, an alkyl naphthalene where the alkyl group is primarily
comprised of 1-hexadecene is used. Other alkylates of aromatics can
be advantageously used. Naphthalene or methyl naphthalene, for
example, can be alkylated with olefins such as octene, decene,
dodecene, tetradecene or higher, mixtures of similar olefins, and
the like. Useful concentrations of hydrocarbyl aromatic in a
lubricant oil composition can be 2% to 25%, preferably 4% to 20%,
and more preferably 4% to 15%, depending on the application.
[0069] Alkylated aromatics such as the hydrocarbyl aromatics of the
present disclosure may be produced by well-known Friedel-Crafts
alkylation of aromatic compounds. See Friedel-Crafts and Related
Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York,
1963. For example, an aromatic compound, such as benzene or
naphthalene, is alkylated by an olefin, alkyl halide or alcohol in
the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and
Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See
Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many
homogeneous or heterogeneous, solid catalysts are known to one
skilled in the art. The choice of catalyst depends on the
reactivity of the starting materials and product quality
requirements. For example, strong acids such as AlCl.sub.3,
BF.sub.3, or HF may be used. In some cases, milder catalysts such
as FeCl.sub.3 or SnCl.sub.4 are preferred. Newer alkylation
technology uses zeolites or solid super acids.
[0070] Esters comprise a useful base stock. 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, alkyl succinic acid, alkenyl succinic
acid, maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acid, alkenyl malonic acid, 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.
[0071] Particularly useful synthetic esters may be 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 acid, lauric acid, myristic acid, palmitic
acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid, or mixtures of any of these materials.
[0072] Suitable synthetic ester components include the esters of
trimethylol propane, trimethylol butane, trimethylol ethane,
pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from 5 to 10 carbon atoms. These
esters are widely available commercially, for example, the Mobil
P-41 and P-51 esters of ExxonMobil Chemical Company.
[0073] Also useful are esters derived from renewable material such
as coconut, palm, rapeseed, soy, sunflower and the like. These
esters may be monoesters, di-esters, polyol esters, complex esters,
or mixtures thereof. These esters are widely available
commercially, for example, the Mobil P-51 ester of ExxonMobil
Chemical Company.
[0074] Other useful fluids of lubricating viscosity include
non-conventional or unconventional base stocks that have been
processed, preferably catalytically, or synthesized to provide high
performance lubrication characteristics.
[0075] Non-conventional or unconventional base stocks/base oils
include one or more of a mixture of base stock(s) derived from one
or more Gas-to-Liquids (GTL) materials, as well as
isomerate/isodewaxate base stock(s) derived from natural wax or
waxy feeds, mineral and or non-mineral oil waxy feed stocks such as
slack waxes, natural waxes, and waxy stocks such as gas oils, waxy
fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal
crackates, or other mineral, mineral oil, or even non-petroleum oil
derived waxy materials such as waxy materials received from coal
liquefaction or shale oil, and mixtures of such base stocks.
[0076] 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.
[0077] 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/s 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).
[0078] 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.
[0079] 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.
[0080] 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).
[0081] 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.
[0082] Base oils for use in the formulated lubricating greases
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.
[0083] The lubricating base oil or base stock constitutes the major
component of the grease lubricant composition of the present
disclosure. One particularly preferred lubricating oil base stock
for the inventive lubricating grease and the inventive method for
improving high temperature bearing performance is a Group I base
stock that is included in the formulated oil at from 75 to 95 wt %,
or from 80 to 90 wt %, or from 82 to 88 wt %. Another particularly
preferred lubricating oil base stock for the inventive lubricating
engine oil and the inventive method for improving fuel efficiency,
frictional properties and deposit control is a combination of a
Group III, Group IV and Group V base stock wherein the combination
is included in the formulated oil at from 75 to 95 wt %, or from 80
to 90 wt %, or from 82 to 88 wt %. In this form, the Group III base
stock is included at from 30 to 35 wt % or from 32 to 33 wt %, the
Group IV base stock at from 45 to 55 wt % or from 48 to 52 wt %,
and the Group V base stock at from 0 to 5 wt %, or from 2 to 4 wt
%.
[0084] Preferred Group III base stocks are GTL and Yubase Plus
(hydroprocessed base stock). Preferred Group V base stocks include
alkylated naphthalene, synthetic esters and combinations
thereof.
[0085] Lubricating oils and base stocks are disclosed for example
In US. Pub. Nos. 20170211007, 20150344805 and 2015322367.
[0086] Grease Thickener
[0087] The compositions of the present disclosure may include a
thickener (e.g., a water-insoluble thickener) in a range from about
0.5 to about 20 wt. % (e.g., about 0.5 to about 10 wt. %. For
example, the grease composition of the present disclosure may have
thickener present in an amount of about 0.5 wt. % to about 20 wt.
%, about 0.5 wt. % to about 17.5 wt. %, about 0.5 wt. % to about 15
wt. %, about 0.5 wt. % to about 12.5 wt. %, about 0.5 wt. % to
about 10 wt. %, about 0.5 wt. % to about 7.5 wt. %, about 0.5 wt. %
to about 5 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to
about 17.5 wt. %, about 1 wt. % to about 15 wt. %, about 1 wt. % to
about 12.5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to
about 7.5 wt. %, about 1 wt. % to about 5 wt. %, about 2.5 wt. % to
about 20 wt. %, about 2.5 wt. % to about 17.5 wt. %, about 2.5 wt.
% to about 15 wt. %, about 2.5 wt. % to about 12.5 wt. %, about 2.5
wt. % to about 10 wt. %, about 2.5 wt. % to about 7.5 wt. %, about
5 wt. % to about 20 wt. %, about 5 wt. % to about 17.5 wt. %, about
5 wt. % to about 15 wt. %, about 5 wt. % to about 12.5 wt. %, about
5 wt. % to about 10 wt. %, about 7.5 wt. % to about 20 wt. %, about
7.5 wt. % to about 17.5 wt. %, about 7.5 wt. % to about 15 wt. %,
about 7.5 wt. % to about 12.5 wt. %, about 10 wt. % to about 20 wt.
%, about 10 wt. % to about 17.5 wt. %, about 10 wt. % to about 15
wt. %, about 12.5 wt. % to about 20 wt. %, about 12.5 wt. % to
about 17.5 wt. %, or about 15 wt. % to about 20 wt. %.
[0088] The grease will contain an essentially water- and
oil-insoluble thickener to provide the desired grease consistency
and structure (cone penetration, dropping point, etc.). Thickeners
may be of the soap or non-soap types. Non-soaps are based on
organic or non-organic solids such as bentonite clay, polymers such
as the polyureas or silica aerogels and may be used where their
particular properties so indicate. For example, thickeners for the
present greases are the metal salt/soap thickeners, including the
complex soap thickeners based on metals including aluminum, barium,
calcium, lithium, sodium. These types of thickeners are well
established and are described in numerous publications. See, for
example, Boner op cit, Lubricants and Related Products, Klamann,
Verlag Chemie, 1984, ISBN 3-527-26022-6, ISBN 0-89573-177-0 to
which reference is made for a description of suitable thickeners
and the manufacture of grease incorporating them.
[0089] Complex grease thickeners are made by combining the
conventional metallic soaps with a complexing agent. The soaps may
be a metal salt of a long chain fatty acid having from 8 to 24
carbon atoms such as decanoic acid, myristic acid, palmitic acid or
stearic acid. The thickener may be a lithium or lithium complex
thickener that incorporates a hydroxy fatty acid having from 12 to
24 (e.g., from 16 to 20) carbon atoms. For example, the hydroxy
fatty acid may be an hydroxy stearic acid, e.g., 9-hydroxy or
10-hydroxy stearic acid, or 12-hydroxy stearic acid. Other hydroxyl
fatty acids which may be used include ricinoleic acid
(12-hydroxystearic acid unsaturated at the 9,10 position),
12-hydroxybehenic acid and 10-hydroxypalmitic acid. The complex
salt/soap thickeners are made with a combination of conventional
lithium soap such as lithium 12-hydroxystearate and a complexing
agent which may vary with the type of thickener, e.g. calcium
complex thickeners may be formulated with acetic acid and
hydroxy-substituted acids; boric acid may be used with lithium
soaps. Low molecular-weight organic acid, typically C.sub.4 to
C.sub.12 dibasic acids such as glutaric, azelaic, pimelic, suberic,
adipic or sebacic acids, are generally favored as the complexing
agents with lithium greases. The complexes are formed by the
introduction of the complexing agent or its metal salt into the
lattice of the metal salt. Examples of metal salt/soap complex
thickeners are described in U.S. Pat. Nos. 3,929,651; 3,940,339;
4,410,435; 4,444,669 and 5,731,274. The complexing agent may be
added as the free acid, a salt e.g., the lithium salt or as an
ester such as an alkyl ester, e.g. methyl glutarate or methyl
adipate, which will undergo hydrolysis to the acid in the presence
of the added alkali, e.g. lithium hydroxide, to form the complexing
agent. PAO bases may require a higher proportion of thickener than
mineral oil base stocks.
[0090] The lithium complex thickener used in the grease of the
present disclosure is not particularly limited and can be any
lithium complex thickener that is known or that becomes known. For
example, the lithium complex thickener can comprise a lithium soap
derived from a fatty acid having: (a) (i) at least one of an epoxy
group, ethylenic unsaturation, or a combination thereof, and (ii) a
dilithium salt derived from a straight chain dicarboxylic acid;
and/or (b) a lithium salt derived from a hydroxy-substituted
carboxylic acid, e.g. salicylic acid.
[0091] For example, the lithium complex thickener can comprise at
least one of: a complex of a lithium soap of a C.sub.12 to C.sub.24
hydroxy fatty acid and a monolithium salt of boric acid; a lithium
salt of a second hydroxy carboxylic acid, such as salicylic acid;
or a combination thereof.
[0092] The lithium complex thickener can comprise a lithium soap of
a C.sub.12 to C.sub.24 hydroxy fatty acid thickener antioxidant
having an alkali metal salt of hydroxy benzoic acid and a diozime
compound. In certain embodiments, the alkali metal salt of hydroxy
benzoic acid includes dilithium salicylate.
[0093] The lithium complex thickener can be a lithium soap
comprising at least one of: a dilithium salt of a C.sub.4 to
C.sub.12 dicarboxylic acid, e.g., dilithium azelate; a lithium soap
of a 9-, 10- or 12-hydroxy C.sub.12 to C.sub.24 fatty acid, e.g.,
lithium 12-hydroxy stearate; and a lithium salt formed in-situ in
the grease from a second hydroxy carboxylic acid, wherein the --OH
group is attached to a carbon atom not more than 6 carbons removed
from the carboxyl group and either of those groups can be attached
to aliphatic portions of the materials or aromatic portions of the
materials.
[0094] In any aspect or embodiment described herein, the lithium
complex thickener can comprise a complex lithium thickener and at
least one of a lithium salt of a C.sub.3 to C.sub.14
hydroxycarboxylic acid, a thiadiazole, or a combination
thereof.
[0095] In any aspect or embodiment described herein, the water
insoluble thickener may include at least one of an aluminum soap, a
barium soap, a calcium soap, a lithium soap, an aluminum salt/soap
complex, a barium salt/soap complex, a calcium salt/soap complex, a
lithium salt/soap complex, or a combination thereof.
[0096] The lubricating greases of the disclosure may contain one or
more further additives. Further additives may be present, in each
case, from about 0.01 wt %, about 0.1, about 0.5 or about 1 wt % to
about 2 wt %, about 5, about 7, about 8, about 10, about 14, about
17, about 20, about 22 or about 25 wt %, based on the total weight
of the lubricating grease formulation.
[0097] The formulated lubricating grease useful in the present
disclosure may additionally contain one or more of the other
commonly used lubricant performance additives including but not
limited to antiwear agents, dispersants, other detergents,
corrosion inhibitors, rust inhibitors, metal deactivators, extreme
pressure additives, anti-seizure agents, wax modifiers, viscosity
index improvers, viscosity modifiers, fluid-loss additives, seal
compatibility agents, organic metallic 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.
[0098] Reference is also made to "Lubricant Additives" by M. W.
Ranney, published by Noyes Data Corporation of Parkridge, N J
(1973); see also U.S. Pat. No. 7,704,930, the disclosure of which
is incorporated herein in its entirety. These additives are
commonly delivered with varying amounts of diluent oil that may
range from 5 weight percent to 50 weight percent.
[0099] 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.
Performance Additives
[0100] The composition of the present disclosure may include small
amounts of at least one (e.g., 1, 2, 3, 4, 5, or 6, or more)
performance additive. For example, the composition of the present
disclosure may include at least one of anticorrosive agent or
corrosion inhibitor, an extreme pressure additive, an antiwear
agent, a pour point depressants, an antioxidant or oxidation
inhibitor, a rust inhibitor, a metal deactivator, a dispersant, a
demulsifier, a dye or colorant/chromophoric agent, a seal
compatibility agent, a friction modifier, a viscosity
modifier/improver, a viscosity index improver, or combinations
thereof. For example, solid lubricants such as molybdenum disulfide
and graphite may be present in the composition of the present
disclosure, such as from about 1 to about 5 wt. % (e.g., from about
1.5 to about 3 wt. %) for molybdenum disulfide and from about 3 to
about 15.wt. % (e.g., from about 6 to about 12 wt. %) for
graphite.
[0101] The amounts of individual additives will vary according to
the additive and the level of functionality to be provided by
it.
[0102] The presence or absence of these lubricating oil performance
additives does not adversely affect the compositions of the present
disclosure. 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) and "Lubricant Additives:
Chemistry and Applications" edited by L. R. Rudnick, published by
CRC Press of Boca Raton, Fla. (2009). The performance additives
useful in the present disclosure do not have to be soluble in the
lubricating oils. Insoluble additives in oil can be dispersed in
the lubricating oils of the present disclosure. The types and
quantities of performance additives used in combination with the
compositions of the present disclosure are not limited by the
examples shown herein as illustrations.
[0103] As such, in any aspect or embodiment described herein, the
composition further comprises at least one of anticorrosive agent
or corrosion inhibitor, an extreme pressure additive, an antiwear
agent, a pour point depressants, an antioxidant or oxidation
inhibitor, a rust inhibitor, a metal deactivator, a dispersant, a
demulsifier, a dye or colorant/chromophoric agent, a seal
compatibility agent, a friction modifier, a viscosity
modifier/improver, a viscosity index improver, or combinations
thereof. In any aspect or embodiment described herein, the
dispersant includes succinimide-type dispersant. Unless specified
otherwise, the performance additive or performance additives listed
above are present in a total amount equal to or less than about 10
wt. %, equal to or less than about 9.5 wt. %, equal to or less than
about 9 wt. %, equal to or less than about 8.5 wt. %, equal to or
less than about 8 wt. %, equal to or less than about 7.5 wt. %,
equal to or less than about 7 wt. %, equal to or less than about
6.5 wt. %, equal to or less than about 6 wt. %, equal to or less
than about 5.5 wt. %, equal to or less than about 5 wt. %, equal to
or less than about 4.5 wt. %, equal to or less than about 4 wt. %,
equal to or less than about 3.5 wt. %, equal to or less than about
3 wt. %, equal to or less than about 2.5 wt. %, equal to or less
than about 2 wt. %, equal to or less than about 1.5 wt. %, or equal
to or less than about 0.5 wt. %. For example, the performance
additive or performance additives are present in a total amount of
about 0.1 to about 10 wt. %, about 0.1 to about 9 wt. %, about 0.1
to about 8 wt. %, about 0.1 to about 7 wt. %, about 0.1 to about 6
wt. %, about 0.1 to about 5 wt. %, about 0.1 to about 4 wt. %,
about 0.1 to about 3 wt. %, about 0.1 to about 2 wt. %, about 0.1
to about 1 wt. %, about 0.5 to about 10 wt. %, about 0.5 to about 9
wt. %, about 0.5 to about 8 wt. %, about 0.5 to about 7 wt. %,
about 0.5 to about 6 wt. %, about 0.5 to about 5 wt. %, about 0.5
to about 4 wt. %, about 0.5 to about 3 wt. %, about 0.5 to about 2
wt. %, about 1 to about 10 wt. %, about 1 to about 9 wt. %, about 1
to about 8 wt. %, about 1 to about 7 wt. %, about 1 to about 6 wt.
%, about 1 to about 5 wt. %, about 1 to about 4 wt. %, about 1 to
about 3 wt. %, about 2 to about 10 wt. %, about 2 to about 9 wt. %,
about 2 to about 8 wt. %, about 2 to about 7 wt. %, about 2 to
about 6 wt. %, about 2 to about 5 wt. %, about 2 to about 4 wt. %,
about 3 to about 10 wt. %, about 3 to about 9 wt. %, about 3 to
about 8 wt. %, about 3 to about 7 wt. %, about 3 to about 6 wt. %,
about 3 to about 5 wt. %, about 4 to about 10 wt. %, about 4 to
about 9 wt. %, about 4 to about 8 wt. %, about 4 to about 7 wt. %,
about 4 to about 6 wt. %, about 5 to about 10 wt. %, about 5 to
about 9 wt. %, about 5 to about 8 wt. %, about 5 to about 7 wt. %,
about 6 to about 10 wt. %, about 6 to about 9 wt. %, about 6 to
about 8 wt. %, about 7 to about 10 wt. %, about 7 to about 9 wt. %,
or about 8 to about 10 wt. %.
[0104] When the additives are described below by reference to
individual components used in the formulation, they will not
necessarily be present or identifiable as discrete entities in the
final product but may be present as reaction products which are
formed during the grease manufacture or even its use. This will
depend on the respective chemistries of the ingredients, their
stoichiometry, and the temperatures encountered in the grease
making process or during its use. It will also depend, naturally
enough, on whether or not the species are added as a pre-reacted
additive package. For example, the acid amine phosphates may be
added as discrete amines and acid phosphates but these may react to
form a new entity in the final grease composition under the
processing conditions used in the grease manufacture.
[0105] Viscosity Improver(s) or Modifier(s).
[0106] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one
viscosity improver or modifier (e.g., 1, 2, 3, 4, 5, 6, or more
viscosity improver or modifier). The viscosity improver, viscosity
modifier, or Viscosity Index (VI) modifier increases the viscosity
of the composition of the present disclosure at elevated
temperatures, thereby increasing film thickness, and having limited
effects on the viscosity of the composition of the present
disclosure at low temperatures. In certain embodiments, the
composition of the present disclosure comprises at least one
viscosity improver (e.g., 1, 2, 3, 4, 5, 6, or more viscosity
improver(s)). Any viscosity improver that is known or that becomes
known in the art may be utilized in the composition of the present
disclosure. Exemplary viscosity improvers include high molecular
weight hydrocarbons, polyesters and viscosity index improver
dispersants that function as both a viscosity index improver and a
dispersant. The molecular weight of these polymers can range from
about 1,000 to about 1,500,000 (e.g., about 20,000 to about
1,200,000 or about 50,000 to about 1,000,000). In a particular
embodiment, the molecular weights of these polymers can range from
about 1,000 to about 1,000,000 (e.g., about 1,200 to about 500,000
or about 1,200 to about 5,000).
[0107] In certain embodiments, the viscosity improver is at least
one of linear or star-shaped polymers of methacrylate, linear or
star-shaped copolymers of methacrylate, butadiene, olefins,
alkylated styrenes, polyisobutylene, polymethacrylate (e.g.,
copolymers of various chain length alkyl methacrylates), copolymers
of ethylene and propylene, hydrogenated block copolymers of styrene
and isoprene, or combinations thereof. For example, the viscosity
improver may include styrene-isoprene or styrene-butadiene based
polymers of about 50,000 to about 200,000 molecular weight.
[0108] Olefin copolymers are commercially available from Chevron
Oronite Company LLC under the trade designation "PARATONE.RTM."
(such as "PARATONE.RTM. 8921" and "PARATONE.RTM. 8941"); from Afton
Chemical Corporation under the trade designation "HiTEC.RTM." (such
as "HiTEC.RTM. 5850B"); and from The Lubrizol Corporation under the
trade designation "Lubrizol.RTM. 7067C". Hydrogenated polyisoprene
star polymers are commercially available from Infineum
International Limited, e.g., under the trade designation "SV200"
and "SV600". Hydrogenated diene-styrene block copolymers are
commercially available from Infineum International Limited, e.g.,
under the trade designation "SV 50".
[0109] The polymethacrylate or polyacrylate polymers can be linear
polymers which are available from Evnoik Industries under the trade
designation "Viscoplex.RTM." (e.g., Viscoplex 6-954) or star
polymers which are available from Lubrizol Corporation under the
trade designation Asteric.TM. (e.g., Lubrizol 87708 and Lubrizol
87725).
[0110] Illustrative vinyl aromatic-containing polymers useful in
the present disclosure may be derived predominantly from vinyl
aromatic hydrocarbon monomer. Illustrative vinyl
aromatic-containing copolymers useful in the present disclosure may
be represented by the following formula:
A-B,
wherein: [0111] A is a polymeric block derived predominantly from
vinyl aromatic hydrocarbon monomer, and [0112] B is a polymeric
block derived predominantly from conjugated diene monomer.
[0113] Although their presence is not required to obtain the
benefit of the composition of the present disclosure, viscosity
modifiers may be used in an amount of less than about 10 weight
percent (e.g. less than about 7 weight percent or less than about 4
weight percent). In certain embodiments, the viscosity improver is
present in an amount less than 2 weight percent, less than about 1
weight percent, or less than about 0.5 weight percent, based on the
total weight of the composition of the present disclosure.
Viscosity modifiers are generally added as concentrates, in large
amounts of diluent oil.
[0114] As used herein, the viscosity modifier concentrations are
given on an "as delivered" basis. The active polymer may be
delivered with a diluent oil. The "as delivered" viscosity modifier
may contain from about 20 weight percent to about 75 weight percent
of an active polymer for polymethacrylate or polyacrylate polymers,
or from about 8 weight percent to about 20 weight percent of an
active polymer for olefin copolymers, hydrogenated polyisoprene
star polymers, or hydrogenated diene-styrene block copolymers, in
the "as delivered" polymer concentrate.
[0115] Antioxidant(s).
[0116] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one
antioxidant (e.g., 1, 2, 3, 4, 5, 6, or more antioxidant(s)). The
antioxidant(s) may be added to retard the oxidative degradation of
the composition in storage or during service. Such degradation may
result in deposits on metal surfaces, the presence of sludge, or a
viscosity increase in the lubricant. One skilled in the art knows a
wide variety of oxidation inhibitors that are useful in lubricating
oil compositions. See, Klamann in Lubricants and Related Products,
op cite, and U.S. Pat. Nos. 4,798,684 and 5,084,197, for example.
Any antioxidant that is known or that becomes known in the art may
be utilized in the composition of the present disclosure.
[0117] Two general types of oxidation inhibitors are those that
react with the initiators, peroxy radicals, and hydroperoxides to
form inactive compounds, and those that decompose these materials
to form less active compounds. Examples are hindered (alkylated)
phenols, e.g. 6-di(tert-butyl)-4-methylphenol
[2,6-di(tert-butyl)-p-cresol, DBPC], and aromatic amines, e.g.
N-phenyl-.alpha.-naphthalamine. These oxidation inhibitors are used
in turbine, circulation, and hydraulic oils that are intended for
extended service.
[0118] The antioxidant or antioxidants may be present in an amount
equal to or less than about 6 wt. %, equal to or less than about
5.75 wt. %, equal to or less than about 5.5 wt. %, equal to or less
than about 5.25 wt. %, equal to or less than about 5 wt. %, equal
to or less than about 4.75 wt. %, equal to or less than about 4.5
wt. %, equal to or less than about 4.25 wt. %, equal to or less
than about 4 wt. %, equal to or less than about 3.75 wt. %, equal
to or less than about 3.5 wt. %, equal to or less than about 3.25
wt. %, equal to or less than about 3 wt. %, equal to or less than
about 2.75 wt. %, equal to or less than about 2.5 wt. %, equal to
or less than about 2.25 wt. %, equal to or less than about 2 wt. %,
equal to or less than about 1.75 wt. %, equal to or less than about
1.5 wt. %, equal to or less than about 1.25 wt. %, equal to or less
than about 1 wt. %, equal to or less than about 0.75 wt. %, equal
to or less than about 0.50 wt. %, or equal to or less than about
0.25 wt. % on an as-received basis. For example, the antioxidant or
antioxidants may be present in an amount of about 0.1 wt. % to
about 6 wt. %, about 0.1 wt. % to about 5 wt. %, about 0.1 wt. % to
about 4 wt. %, about 0.1 wt. % to about 3 wt. %, about 0.1 wt. % to
about 2 wt. %, about 0.1 wt. % to about 1.5 wt. %, about 0.1 wt. %
to about 1 wt. %, about 0.1 wt. % to about 0.75 wt. %, about 0.1
wt. % to about 0.5 wt. %, about 0.2 wt. % to about 6 wt. %, about
0.2 wt. % to about 5 wt. %, about 0.2 wt. % to about 4 wt. %, about
0.2 wt. % to about 3 wt. %, about 0.2 wt. % to about 2 wt. %, about
0.2 wt. % to about 1.5 wt. %, about 0.2 wt. % to about 1 wt. %,
about 0.2 wt. % to about 0.75 wt. %, about 0.2 wt. % to about 0.5
wt. %, about 0.3 wt. % to about 6 wt. %, about 0.3 wt. % to about 5
wt. %, about 0.3 wt. % to about 4 wt. %, about 0.3 wt. % to about 3
wt. %, about 0.3 wt. % to about 2 wt. %, about 0.3 wt. % to about
1.5 wt. %, about 0.3 wt. % to about 1 wt. %, about 0.3 wt. % to
about 0.75 wt. %, about 0.3 wt. % to about 0.5 wt. %, about 0.5 wt.
% to about 6 wt. %, about 0.5 wt. % to about 5 wt. %, about 0.5 wt.
% to about 4 wt. %, about 0.5 wt. % to about 3 wt. %, about 0.5 wt.
% to about 2 wt. % about 0.5 wt. % to about 1.5 wt. %, about 0.5
wt. % to about 1 wt. %, about 0.5 wt. % to about 0.75 wt. %, about
0.5 wt. % to about 0.5 wt. %, about 1 wt. % to about 6 wt. %, about
1 wt. % to about 5 wt. %, about 1 wt. % to about 4 wt. %, about 1
wt. % to about 3 wt. %, about 2 wt. % to about 6 wt. %, about 2 wt.
% to about 5 wt. %, about 2 wt. % to about 4 wt. %, about 3 wt. %
to about 6 wt. %, about 3 wt. % to about 5 wt. %, about 4 wt. % to
about 6 wt. %, or about 5 wt. % to about 6 wt. % on an as-received
basis.
[0119] The below discussion of phenolic antioxidants is presented
only by way of example, and is not limiting on the type of phenolic
antioxidants that can be utilized in the composition of the present
disclosure.
[0120] Useful antioxidants include hindered phenols. These phenolic
antioxidants may be ashless (metal-free) phenolic compounds or
neutral or basic metal salts of certain phenolic compounds. In an
embodiment, the phenolic antioxidant compounds or compounds are
hindered phenolics which are the ones which contain a sterically
hindered hydroxyl group, such as those that are derivatives of
dihydroxy aryl compounds in which the hydroxyl groups are in the o-
or p-position to each other. In certain embodiments, the phenolic
antioxidant or antioxidants are hindered phenols substituted with
C6+ 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; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful
hindered mono-phenolic antioxidants may include for example
hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
Bis-phenolic antioxidants may also be advantageously used in
combination with the composition of the present disclosure.
Examples of ortho-coupled phenols include:
2,2'-bis(4-heptyl-6-t-butyl-phenol);
2,2'-bis(4-octyl-6-t-butyl-phenol); and
2,2'-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols
include for example 4,4'-bis(2,6-di-t-butyl phenol) and
4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0121] Further examples of phenol-based antioxidants include
2-t-butylphenol, 2-t-butyl-4-methylphenol,
2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol,
2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (manufactured
by the Kawaguchi Kagaku Co. under trade designation "Antage DBH"),
2,6-di-t-butylphenol and 2,6-di-t-butyl-4-alkylphenols such as
2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol;
2,6-di-t-butyl-4-alkoxyphenols such as
2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol,
3,5-di-t-butyl-4-hydroxybenzylmercaptoocty-1 acetate,
alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such as
n-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yonox
SS"), n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;
2,6-di-t-butyl-alpha-dimethylamino-p-cresol,
2,2'-methylenebis(4-alkyl-6-t-butylphenol) compounds such as
2,2'-methylenebis(4-methyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-400")
and 2,2'-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage W-500");
bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butyl-phenol)
(manufactured by the Kawaguchi Kagaku Co. under the trade
designation "Antage W-300"), and
4,4'-methylenebis(2,6-di-t-butylphenol) (manufactured by Laporte
Performance Chemicals under the trade designation "Ionox
220AH").
[0122] Other examples of phenol-based antioxidants include
4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane
(Bisphenol A), 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-di-t-butylphenol), hexamethylene glycol
bis[3, (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by
the Ciba Specialty Chemicals Co. under the trade designation
"Irganox L109"), triethylene glycol
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Tominox
917"),
2,2'-thio[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
(manufactured by the Ciba Specialty Chemicals Co. under the trade
designation "Irganox L115"), 3,9-bis
{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]ethy-
l}2,4,8,10-tetraoxaspiro[5,5]undecane (manufactured by the Sumitomo
Kagaku Co. under the trade designation "Sumilizer GA80") and
4,4'-thiobis(3-methyl-6-t-butylphenol) (manufactured by the
Kawaguchi Kagaku Co. under the trade designation "Antage RC"),
2,2'-thiobis(4,6-di-t-butylresorcinol); polyphenols, such as
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionato]methane
(manufactured by the Ciba Specialty Chemicals Co. under the trade
designation "Irganox L101"),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (manufactured
by the Yoshitomi Seiyaku Co. under the trade designation "Yoshinox
930"),
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene
(manufactured by Ciba Specialty Chemicals under the trade
designation "Irganox 330"),
bis[3,3'-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid] glycol
ester,
2-(3',5'-di-t-butyl-4-hydroxyphenyl)-methyl-4-(2'',4''-di-t-butyl-3''-hyd-
roxyphenyl)methyl-6-t-butylphenol and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol; and
phenol/aldehyde condensates, such as the condensates of
p-t-butylphenol and formaldehyde and the condensates of
p-t-butylphenol and acetaldehyde.
[0123] The phenolic antioxidant or phenolic type antioxidant
include sulfurized and non-sulfurized phenolic antioxidants.
Phenolic antioxidants include 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 antioxidants include
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 may include mono- and poly-alkyl or
alkenyl phenols, the alkyl or alkenyl group containing from about 3
to about 100 carbons (e.g., about 4 to about 50 carbons) and
sulfurized derivatives thereof. The number of alkyl or alkenyl
groups present in the aromatic ring may range from 1 up to the
available unsatisfied valences of the aromatic ring remaining after
counting the number of hydroxyl groups bound to the aromatic
ring.
[0124] For example, the phenolic antioxidant may be represented by
the following formula:
(R).sub.x--Ar--(OH).sub.y,
wherein:
[0125] Ar is selected from the group consisting of:
##STR00006##
wherein: R is a C.sub.3-C.sub.100 alkyl or alkenyl group, a sulfur
substituted alkyl or alkenyl group (e.g., a C.sub.4-C.sub.50 alkyl
or alkenyl group or sulfur substituted alkyl or alkenyl group, a
C.sub.3-C.sub.100 alkyl or sulfur substituted alkyl group, or 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 (e.g., a
C.sub.2-C.sub.50 alkylene or sulfur substituted alkylene group or 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; m is 0 to 4; and p is 0 or 1.
[0126] In certain embodiments, at least one of: R is
C.sub.4-C.sub.50 alkyl group, R.sup.g is a C.sub.2-C.sub.20
alkylene or sulfur substituted alkylene group, y ranges from 1 to
3, x ranges from 0 to 3, z ranges from 1 to 4, n ranges from 0 to
5, p is 0, or a combination thereof.
[0127] In particular embodiments, the phenolic antioxidant include
hindered phenolics and phenolic esters that contain a sterically
hindered hydroxyl group. For example, the phenolic antioxidant can
include derivatives of dihydroxy aryl compounds in which the
hydroxyl groups are in the o- or p-position to each other. The
phenolic antioxidant may include the hindered phenols substituted
with C.sub.1+ alkyl groups and the alkylene coupled derivatives of
these hindered phenols, such as: 2-t-butyl-4-heptyl phenol;
2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;
2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;
2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl
phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl
phenol; 2,6-di-t-butyl 4 alkoxy phenol; and/or
##STR00007##
[0128] In certain embodiments, the phenolic type antioxidant is at
least one of Ethanox.RTM. 4710, Irganox.RTM. 1076, Irganox.RTM.
L1035, Irganox.RTM. 1010, Irganox.RTM. L109, Irganox.RTM. L118,
Irganox.RTM. L135, or a combination thereof.
[0129] The phenolic antioxidant or antioxidants may be present in
an amount of about 0.05 wt. % to about 3 wt. %, about 0.05 wt. % to
about 2.5 wt. %, about 0.05 wt. % to about 2 wt. %, about 0.05 wt.
% to about 1.5 wt. %, about 0.05 wt. % to about 1 wt. %, about 0.05
wt. % to about 0.75 wt. %, about 0.05 wt. % to about 0.5 wt. %,
about 0.05 wt. % to about 0.3 wt. %, about 0.1 wt. % to about 3 wt.
%, about 0.1 wt. % to about 2.5 wt. %, about 0.1 wt. % to about 2
wt. %, about 0.1 wt. % to about 1.5 wt. %, about 0.1 wt. % to about
1 wt. %, about 0.1 wt. % to about 0.75 wt. %, about 0.1 wt. % to
about 0.5 wt. %, about 0.1 wt. % to about 0.3 wt. %, about 0.5 wt.
% to about 3 wt. %, about 0.5 wt. % to about 2.5 wt. %, about 0.5
wt. % to about 2 wt. %, about 0.5 wt. % to about 1.5 wt. %, about
0.5 wt. % to about 1 wt. %, about 1 wt. % to about 3 wt. %, about 1
wt. % to about 2.5 wt. %, about 1 wt. % to about 2 wt. %, about 1
wt. % to about 1.75 wt. %, about 1 wt. % to about 1.5 wt. %, about
1.5 wt. % to about 3 wt. %, about 1.5 wt. % to about 2.5 wt. %,
about 1.5 wt. % to about 2 wt. %, about 2 wt. % to about 3 wt. %,
about 2 wt. % to about 2.5 wt. %, or about 2.5 wt. % to about 3 wt.
%, on an as-received basis.
[0130] Effective amounts of one or more catalytic antioxidants may
be used. The catalytic antioxidants comprise an effective amount of
a) one or more oil soluble polymetal organic compounds; and,
effective amounts of b) one or more substituted
N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered
phenol compounds; or a combination of both b) and c). Catalytic
antioxidants are more fully described in U.S. Pat. No. 8,048,833,
which is incorporated herein by reference in its entirety.
[0131] Non-phenolic oxidation inhibitors that may be used in the
composition of the present disclosure include aromatic amine
antioxidants, which may be used either as such or in combination
with phenolic antioxidants.
[0132] An exemplary aromatic amine antioxidant include alkylated
and non-alkylated aromatic amines, such as aromatic monoamines of
the formula
R.sup.1R.sup.2R.sup.3N,
wherein: R.sup.1 is an aliphatic, aromatic or substituted aromatic
group; R.sup.2 is an aromatic or a substituted aromatic group;
R.sup.3 is H, alkyl, aryl or R.sup.4S(O).sub.xR.sup.5; R.sup.4 is
an alkylene, alkenylene, or aralkylene group; R.sup.5 is a higher
alkyl group, or an alkenyl, aryl, or alkaryl group; and x is 0, 1
or 2.
[0133] The aliphatic group R.sup.1 may contain from 1 to about 20
carbon atoms (e.g. from about 6 to 12 carbon atoms). The aliphatic
group may be a saturated aliphatic group. In certain embodiments,
both R.sup.1 and R.sup.2 are aromatic or substituted aromatic
groups, and the aromatic group may be a fused ring aromatic group
such as naphthyl. Aromatic groups R.sup.1 and R.sup.2 may be joined
together with other groups such as S.
[0134] The aminic antioxidant may be an aromatic amine antioxidant,
such as an phenyl-.alpha.-naphthyl amine (e.g., Irganox.RTM. L06)
which is described by the following chemical structure:
##STR00008##
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; and n is an integer
ranging from 1 to 5 (e.g. 1).
[0135] In certain embodiments, at least one of: R.sup.z is C.sub.1
to C.sub.10 linear or C.sub.3 to C.sub.10 branched alkyl group; n
is 1; or a combination thereof,
[0136] In another embodiment, R.sup.z is a linear or branched
C.sub.6 to C.sub.8.
[0137] In certain embodiments, the aromatic amine antioxidant can
have at least 6 carbon atoms substituted with an alkyl groups.
Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl,
and decyl. In an embodiments, the aliphatic groups will not contain
more than about 14 carbon atoms. Additional amine antioxidants
include diphenylamines, phenyl naphthylamines, phenothiazines,
imidodibenzyls, and diphenyl phenylene diamines. In a particular
embodiment, a mixture of two or more (e.g., 2, 3, 4, 5, or more)
aromatic amine antioxidants are present in the composition of the
present disclosure. Polymeric amine antioxidants can also be used.
Particular examples of aromatic amine antioxidants useful in the
composition of the present disclosure include:
p,p'-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine;
phenyl-alphanaphthylamine; and
p-octylphenyl-alpha-naphthylamine.
[0138] Further examples of amine-based antioxidants include
dialkyldiphenylamines, such as p,p'-dioctyldiphenylamine
(manufactured by the Seiko Kagaku Co. under the trade designation
"Nonflex OD-3"), p,p'-di-alpha-methylbenzyl-diphenylamine and
N-p-butylphenyl-N-p'-octylphenylamine; monoalkyldiphenylamines,
such as mono-t-butyldiphenylamine, and monooctyldiphenylamine;
bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and
di(2-ethyl-4-nonylphenyl)amine; alkylphenyl-1-naphthylamines, such
as octylphenyl-1-naphthylamine and
N-t-dodecylphenyl-1-naphthylamine; arylnaphthylamines, such as
1-naphthylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine,
N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine,
phenylenediamines such as N,N'-diisopropyl-p-phenylenediamine and
N,N'-diphenyl-p-phenylenediamine, and phenothiazines such as
phenothiazine (manufactured by the Hodogaya Kagaku Co.:
Phenothiazine) and 3,7-dioctylphenothiazine.
[0139] A sulfur-containing antioxidant may be any and every
antioxidant containing sulfur, for example, including dialkyl
thiodipropionates such as dilauryl thiodipropionate and distearyl
thiodipropionate, dialkyldithiocarbamic acid derivatives (excluding
metal salts), bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide,
mercaptobenzothiazole, reaction products of phosphorus pentoxide
and olefins, and dicetyl sulfide. For example, the
sulfur-containing antioxidant is a dialkyl thiodipropionate, such
as dilauryl thiodipropionate and distearyl thiodipropionate.
[0140] Additional examples of sulphur-based antioxidants include
dialkylsulphides, such as didodecylsulphide and
dioctadecylsulphide; thiodipropionic acid esters, such as didodecyl
thiodipropionate, dioctadecyl thiodipropionate, dimyristyl
thiodipropionate and dodecyloctadecyl thiodipropionate, and
2-mercaptobenzimidazole. In an embodiment, the antioxidant is a
sulfurized alkyl phenols, or an alkali or alkaline earth metal salt
thereof.
[0141] In certain embodiments, the composition of the present
disclosure includes at least one aminic antioxidant (e.g., 1, 2, 3,
4, 5, or more) present in an amount equal to or less than about 6
wt. %, equal to or less than about 5.75 wt. %, equal to or less
than about 5.5 wt. %, equal to or less than about 5.25 wt. %, equal
to or less than about 5 wt. %, equal to or less than about 4.75 wt.
%, equal to or less than about 4.5 wt. %, equal to or less than
about 4.25 wt. %, equal to or less than about 4 wt. %, equal to or
less than about 3.75 wt. %, equal to or less than about 3.5 wt. %,
equal to or less than about 3.25 wt. %, equal to or less than about
3 wt. %, equal to or less than about 2.75 wt. %, equal to or less
than about 2.5 wt. %, equal to or less than about 2.25 wt. %, equal
to or less than about 2 wt. %, equal to or less than about 1.75 wt.
%, equal to or less than about 1.5 wt. %, equal to or less than
about 1.25 wt. %, equal to or less than about 1 wt. %, equal to or
less than about 0.75 wt. %, equal to or less than about 0.50 wt. %,
or equal to or less than about 0.25 wt. % on an as-received basis.
For example, the aminic antioxidant or antioxidants may be present
in an amount of about 0.1 wt. % to about 6 wt. %, about 0.1 wt. %
to about 5 wt. %, about 0.1 wt. % to about 4 wt. %, about 0.1 wt. %
to about 3 wt. %, about 0.1 wt. % to about 2 wt. %, about 0.1 wt. %
to about 1.5 wt. %, about 0.1 wt. % to about 1 wt. %, about 0.1 wt.
% to about 0.75 wt. %, about 0.1 wt. % to about 0.5 wt. %, about
0.2 wt. % to about 6 wt. %, about 0.2 wt. % to about 5 wt. %, about
0.2 wt. % to about 4 wt. %, about 0.2 wt. % to about 3 wt. %, about
0.2 wt. % to about 2 wt. %, about 0.2 wt. % to about 1.5 wt. %,
about 0.2 wt. % to about 1 wt. %, about 0.2 wt. % to about 0.75 wt.
%, about 0.2 wt. % to about 0.5 wt. %, about 0.3 wt. % to about 6
wt. %, about 0.3 wt. % to about 5 wt. %, about 0.3 wt. % to about 4
wt. %, about 0.3 wt. % to about 3 wt. %, about 0.3 wt. % to about 2
wt. %, about 0.3 wt. % to about 1.5 wt. %, about 0.3 wt. % to about
1 wt. %, about 0.3 wt. % to about 0.75 wt. %, about 0.3 wt. % to
about 0.5 wt. %, about 0.5 wt. % to about 6 wt. %, about 0.5 wt. %
to about 5 wt. %, about 0.5 wt. % to about 4 wt. %, about 0.5 wt. %
to about 3 wt. %, about 0.5 wt. % to about 2 wt. %, about 0.5 wt. %
to about 1.5 wt. %, about 0.5 wt. % to about 1 wt. %, about 0.5 wt.
% to about 0.75 wt. %, about 0.5 wt. % to about 0.5 wt. %, about 1
wt. % to about 6 wt. %, about 1 wt. % to about 5 wt. %, about 1 wt.
% to about 4 wt. %, about 1 wt. % to about 3 wt. %, about 2 wt. %
to about 6 wt. %, about 2 wt. % to about 5 wt. %, about 2 wt. % to
about 4 wt. %, about 3 wt. % to about 6 wt. %, about 3 wt. % to
about 5 wt. %, about 4 wt. % to about 6 wt. %, or about 5 wt. % to
about 6 wt. % on an as-received basis.
[0142] Other oxidation inhibitors that have proven useful in
compositions of the present disclosure are chlorinated aliphatic
hydrocarbons such as chlorinated wax; organic sulfides and
polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide,
dibutyl tetrasulfide, sulfurized methyl ester of oleic acid,
sulfurized alkylphenol, sulfurized dipentene, and sulfurized
terpene; phosphosulfurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl oleate,
phosphorus esters including principally dihydrocarbon and
trihydrocarbon phosphites such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,
dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl phosphite,
diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such
as zinc dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,
barium di(heptylphenyl)(phosphorodithioate, cadmium
dinonylphosphorodithioate, and the reaction of phosphorus
pentasulfide with an equimolar mixture of isopropyl alcohol,
4-methyl-2-pentanol, and n-hexyl alcohol.
[0143] Another class of antioxidants which may be used in the
lubricating oil compositions disclosed herein are oil soluble
copper compounds. Any oil soluble suitable copper compound may be
blended into the composition of the present disclosure. Examples of
suitable copper antioxidants include copper dihydrocarbyl thio- or
dithio-phosphates and copper salts of carboxylic acid (naturally
occurring or synthetic). Other suitable copper salts include copper
dithiacarbamates, sulphonates, phenates, and acetylacetonates.
Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived
from alkenyl succinic acids or anhydrides are known to be
particularly useful.
[0144] In an embodiment, the antioxidant includes hindered phenols,
arylamines, or a combination thereof. These antioxidants may be
used individually by type or in combination with one another.
[0145] Pour Point Depressant(s).
[0146] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, 4, 5, or 6, or more) pour point depressant or a lube oil
flow improver. Pour point depressant may be added to lower the
minimum temperature at which the fluid will flow or can be poured.
Any pour point depressant or lube oil flow improved that is known
or that becomes known in the art may be utilized in the composition
of the present disclosure. In certain embodiments, the pour point
depressant includes at least one (e.g., 1, 2, 3, or 4 or more) pour
point depressant or lube oil flow improver, such as at least one of
alkylated naphthalenes polymethacrylates (e.g., copolymers of
various chain length alkyl methacrylates), polyacrylates,
polyarylamides, condensation products of haloparaffin waxes and
aromatic compounds, vinyl carboxylate polymers, terpolymers of
dialkylfumarates, vinyl esters of fatty acids, allyl vinyl ethers,
or combinations thereof. U.S. Pat. Nos. 1,815,022; 2,015,748;
2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2,721,878;
and 3,250,715 describe useful pour point depressants and/or the
preparation thereof. The pour point depressant or depressants may
be present in an amount equal to or less than about 5 wt. %, for
example about 0.01 to about 1.5 wt. %. For example, the pour point
depressant or depressants may be present in an amount equal to or
less than about 5 wt. %, equal to or less than about 4.75 wt. %,
equal to or less than about 4.5 wt. %, equal to or less than about
4.25 wt. %, equal to or less than about 4 wt. %, equal to or less
than about 3.75 wt. %, equal to or less than about 3.5 wt. %, equal
to or less than about 3.25 wt. %, equal to or less than about 3 wt.
%, equal to or less than about 2.75 wt. %, equal to or less than
about 2.5 wt. %, equal to or less than about 2.25 wt. %, equal to
or less than about 2 wt. %, equal to or less than about 1.75 wt. %,
equal to or less than about 1.5 wt. %, equal to or less than about
1.25 wt. %, equal to or less than about 1 wt. %, equal to or less
than about 0.75 wt. %, equal to or less than about 0.50 wt. %, or
equal to or less than about 0.25 wt. % of the composition of the
present disclosure. For example, the pour point depressant or
depressants may be present in an amount of about 0.1 wt. % to about
5 wt. %, about 0.1 wt. % to about 4 wt. %, about 0.1 wt. % to about
3 wt. %, about 0.1 wt. % to about 2 wt. %, about 0.1 wt. % to about
1.5 wt. %, about 0.1 wt. % to about 1 wt. %, about 0.1 wt. % to
about 0.75 wt. %, about 0.1 wt. % to about 0.5 wt. %, about 0.2 wt.
% to about 5 wt. %, about 0.2 wt. % to about 4 wt. %, about 0.2 wt.
% to about 3 wt. %, about 0.2 wt. % to about 2 wt. %, about 0.2 wt.
% to about 1.5 wt. %, about 0.2 wt. % to about 1 wt. %, about 0.2
wt. % to about 0.75 wt. %, about 0.2 wt. % to about 0.5 wt. %,
about 0.3 wt. % to about 5 wt. %, about 0.3 wt. % to about 4 wt. %,
about 0.3 wt. % to about 3 wt. %, about 0.3 wt. % to about 2 wt. %,
about 0.3 wt. % to about 1.5 wt. %, about 0.3 wt. % to about 1 wt.
%, about 0.3 wt. % to about 0.75 wt. %, about 0.3 wt. % to about
0.5 wt. %, about 0.5 wt. % to about 5 wt. %, about 0.5 wt. % to
about 4 wt. %, about 0.5 wt. % to about 3 wt. %, about 0.5 wt. % to
about 2 wt. %, about 0.5 wt. % to about 1.5 wt. %, about 0.5 wt. %
to about 1 wt. %, about 0.5 wt. % to about 0.75 wt. %, about 0.5
wt. % to about 0.5 wt. %, about 1 wt. % to about 5 wt. %, about 1
wt. % to about 4 wt. %, about 1 wt. % to about 3 wt. %, about 2 wt.
% to about 5 wt. %, about 2 wt. % to about 4 wt. %, or about 3 wt.
% to about 5 wt. % of the composition of the present
disclosure.
[0147] Seal Compatibility Agent(s).
[0148] In other embodiments, the composition comprises of the
present disclosure at least one (e.g., 1, 2, 3, 4, or more) seal
compatibility agent. The seal compatibility agent(s) may be added
to help swell elastomeric seals by causing a chemical reaction in
the fluid or physical change in the elastomer. Any seal
compatibility agent that is known or that becomes know may be
utilized in the composition of the present disclosure. For example,
the seal compatibility agent or agents may include at least one of
organic phosphates, aromatic esters, aromatic hydrocarbons, esters
(e.g. butylbenzyl phthalate), polybutenyl succinic anhydride, or
sulfolane-type seal swell agents (e.g. Lubrizol 730-type seal swell
additives), or combinations thereof. Although their presence is not
required to obtain the benefit of the present disclosure, seal
compatibility additives may be present in an amount of zero to
about 3 weight percent (e.g., about 0.01 to about 2 weight percent)
of the composition of the present disclosure.
[0149] Demulsifier(s).
[0150] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, or 4, or more) demulsifier. The demulsifier may be added
to separate emulsions (e.g., water-in-oil). Any demulsifier that is
known or that becomes know may be utilized in the composition of
the present disclosure. An illustrative demulsifying component is
described in EP-A-330,522. This exemplary demulsifying agent is
obtained by reacting an alkylene oxide with an adduct obtained by
reaction of a bis-epoxide with a polyhydric alcohol. Demulsifiers
are commercially available and may be used in conventional minor
amounts along with other additives such as antifoam agents.
Although their presence is not required to obtain the benefit of
the present disclosure, the emulsifier or emulsifiers may be
present a combined amount less than 1 weight percent (e.g. less
than 0.1 weight percent).
[0151] In certain embodiments, the demulsifying agent includes at
least one of alkoxylated phenols, phenol-formaldehyde resins,
synthetic alkylaryl sulfonates (such as metallic dinonylnaphthalene
sulfonates), or a combination thereof. In an embodiment, a
demulsifing agent is a predominant amount of a water-soluble
polyoxyalkylene glycol having a pre-selected molecular weight of
any value in the range of between about 450 and about 5000 or more.
In an embodiment, the water soluble polyoxyalkylene glycol
demulsifier may also be one produced from alkoxylation of n-butanol
with a mixture of alkylene oxides to form a random alkoxylated
product.
[0152] Polyoxyalkylene glycols useful in the present disclosure may
be produced by a well-known process for preparing polyalkylene
oxide having hydroxyl end-groups by subjecting an alcohol or a
glycol ether and one or more alkylene oxide monomers, such as
ethylene oxide, butylene oxide, or propylene oxide, to form block
copolymers in addition polymerization, while employing a strong
base, such as potassium hydroxide as a catalyst. In such a process,
the polymerization is commonly carried out under a catalytic
concentration of about 0.3 to about 1.0% by mole of potassium
hydroxide to the monomer(s) and at high temperature of about
100.degree. C. to about 160.degree. C. It is well known that the
catalyst potassium hydroxide is, for the most part, bonded to the
chain-end of the produced polyalkylene oxide in a form of alkoxide
in the polymer solution so obtained.
[0153] The soluble polyoxyalkylene glycol emulsifier(s) useful in
the compositions of the present disclosure may also be one produced
from alkoxylation of n-butanol with a mixture of alkylene oxides to
form a random alkoxylated product.
[0154] Corrosion Inhibitor or Anti-Rust Additive.
[0155] In any aspect or embodiment, the composition of the present
disclosure comprises at least one (e.g. 1, 2, 3, 4, or more)
corrosion inhibitor or anti-rust additive. The corrosion inhibitor
or anti-rust additive may be added to protect lubricated metal
surfaces against chemical attack by water or other contaminants. A
wide variety of corrosion inhibitors are commercially available,
and any corrosion inhibitor or anti-rust additive that is known or
that becomes know may be utilized in the composition of the present
disclosure. In an embodiment, the corrosion inhibitor can be a
polar compound that wets the metal surface protecting it with a
film of oil. In another embodiment, the anti-rust additive may
absorb water by incorporating it in a water-in-oil emulsion so that
only the oil touches the surface. In yet a further embodiment, the
corrosion inhibitor chemically adheres to the metal to produce a
non-reactive surface. In certain embodiments, the anti-rust
additive or corrosion inhibitor includes at least one zinc
dithiophosphates, metal phenolates, basic metal sulfonates, a fatty
acid, a fatty acid mixture, amines, or a combination thereof.
[0156] Antirust additives may include (short-chain) alkenyl
succinic acids, partial esters thereof and nitrogen-containing
derivatives thereof; and synthetic alkarylsulfonates, such as metal
dinonylnaphthalene sulfonates. Antirust agents include, for
example, monocarboxylic acids which have from 8 to 30 carbon atoms,
alkyl or alkenyl succinates or partial esters thereof,
hydroxy-fatty acids, which have from 12 to 30 carbon atoms and
derivatives thereof, sarcosines which have from 8 to 24 carbon
atoms and derivatives thereof, amino acids and derivatives thereof,
naphthenic acid and derivatives thereof, lanolin fatty acid,
mercapto-fatty acids, and/or paraffin oxides.
[0157] Examples of monocarboxylic acids (C8-C30), include, for
example, caprylic acid, pelargonic acid, decanoic acid, undecanoic
acid, lauric acid, myristic acid, palmitic acid, stearic acid,
arachic acid, behenic acid, cerotic acid, montanic acid, melissic
acid, oleic acid, docosanic acid, erucic acid, eicosenic acid, beef
tallow fatty acid, soy bean fatty acid, coconut oil fatty acid,
linolic acid, linoleic acid, tall oil fatty acid, 12-hydroxystearic
acid, laurylsarcosinic acid, myritsylsarcosinic acid,
palmitylsarcosinic acid, stearylsarcosinic acid, oleylsarcosinic
acid, alkylated (C8-C20) phenoxyacetic acids, lanolin fatty acid,
and C8-C24 mercapto-fatty acids.
[0158] Examples of polybasic carboxylic acids include, for example,
the alkenyl (C10-C100) succinic acids indicated in CAS No.
27859-58-1 and ester derivatives thereof, dimer acid,
N-acyl-N-alkyloxyalkyl aspartic acid esters (U.S. Pat. No.
5,275,749).
[0159] Examples of the alkylamines that function as antirust
additives or as reaction products with the above carboxylates to
give amides and the like are represented by primary amines, such as
laurylamine, coconut-amine, n-tridecylamine, myristylamine,
n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine,
n-nonadecylamine, n-eicosylamine, n-heneicosylamine,
n-docosylamine, n-tricosylamine, n-pentacosylamine, oleylamine,
beef tallow-amine, hydrogenated beef tallow-amine and soy
bean-amine. Examples of the secondary amines include dilaurylamine,
di-coconut-amine, di-n-tridecylamine, dimyristylamine,
di-n-pentadecylamine, dipalmitylamine, di-n-pentadecylamine,
distearylamine, di-n-nonadecylamine, di-n-eicosylamine,
di-n-heneicosylamine, di-n-docosylamine, di-n-tricosylamine,
di-n-pentacosyl-amine, dioleylamine, di-beef tallow-amine,
di-hydrogenated beef tallow-amine and di-soy bean-amine.
[0160] Examples of the aforementioned N-alkylpolyalkyenediamines
include: ethylenediamines, such as laurylethylenediamine, coconut
ethylenediamine, n-tridecylethylenediamine-,
myristylethylenediamine, n-pentadecylethylenediamine,
palmitylethylenediamine, n-heptadecylethylenediamine,
stearylethylenediamine, n-nonadecylethylenediamine,
n-eicosylethylenediamine, n-heneicosylethylenediamine,
n-docosylethylendiamine, n-tricosylethylenediamine,
n-pentacosylethylenediamine, oleylethylenediamine, beef
tallow-ethylenediamine, hydrogenated beef tallow-ethylenediamine
and soy bean-ethylenediamine; propylenediamines such as
laurylpropylenediamine, coconut propylenediamine,
n-tridecylpropylenediamine, myristylpropylenediamine,
n-pentadecylpropylenediamine, palmitylpropylenediamine,
n-heptadecylpropylenediamine, stearylpropylenediamine,
n-nonadecylpropylenediamine, n-eicosylpropylenediamine,
n-heneicosylpropylenediamine, n-docosylpropylendiamine,
n-tricosylpropylenediamine, n-pentacosylpropylenediamine,
diethylene triamine (DETA) or triethylene tetramine (TETA),
oleylpropylenediamine, beef tallow-propylenediamine, hydrogenated
beef tallow-propylenediamine and soy bean-propylenediamine;
butylenediamines such as laurylbutylenediamine, coconut
butylenediamine, n-tridecylbutylenediamine-,
myristylbutylenediamine, n-pentadecylbutylenediamine,
stearylbutylenediamine, n-eicosylbutylenediamine,
n-heneicosylbutylenediamine, n-docosylbutylendiamine,
n-tricosylbutylenediamine, n-pentacosylbutylenediamine,
oleylbutylenediamine, beef tallow-butylenediamine, hydrogenated
beef tallow-butylenediamine and soy bean butylenediamine; and
pentylenediamines such as laurylpentylenediamine, coconut
pentylenediamine, myristylpentylenediamine,
palmitylpentylenediamine, stearylpentylenediamine,
oleyl-pentylenediamine, beef tallow-pentylenediamine, hydrogenated
beef tallow-pentylenediamine and soy bean pentylenediamine.
[0161] The corrosion inhibitor or anti-rust additive may be present
in an amount equal to or less than about 5 wt. %, for example about
0.01 to 5 wt. %, on an as-received basis. For example, the
corrosion inhibitor may be present in an amount equal to or less
than 4 wt. %, equal or less than 3 wt. %, equal to or less than 2
wt. %, or equal to or less than 1 wt. % on an as-received basis. By
way of further example, the corrosion inhibitor may be present in
an amount of about 0.01 to about 5 wt. %, about 0.01 to about 4 wt.
%, about 0.01 to about 3 wt. %, about 0.01 to about 2 wt. %, about
0.05 to about 5 wt. %, about 0.05 to about 4 wt. %, about 0.05 to
about 3 wt. %, about 0.05 to about 2 wt. %, about 0.1 to about 5
wt. %, about 0.1 to about 4 wt. %, about 0.1 to about 3 wt. %,
about 0.1 to about 2 wt. %, about 1 to about 5 wt. %, about 1 to
about 4 wt. %, about 1 to about 3 wt. %, about 2 to about 5 wt. %,
about 2 to about 4 wt. %, or about 3 to about 5 wt. %, on an
as-received basis.
[0162] Metal Passivator(s), Deactivator(s) and Corrosion
Inhibitor(s).
[0163] In any aspect or embodiment, the composition of the present
disclosure comprises at least one (e.g. 1, 2, 3, 4, 5, or 6, or
more) metal passivator, deactivator, or corrosion inhibitor. This
type of component includes 2,5-dimercapto-1,3,4-thiadiazoles and
derivatives thereof, mercaptobenzothiazoles, alkyltriazoles and
benzotriazoles. Examples of dibasic acids useful as anti-corrosion
agents, other than sebacic acids, which may be used in the present
disclosure, are adipic acid, azelaic acid, dodecanedioic acid,
3-methyladipic acid, 3-nitrophthalic acid, 1,10-decanedicarboxylic
acid, and fumaric acid. The anti-corrosion combination is a
straight or branch-chained, saturated or unsaturated monocarboxylic
acid or ester thereof which may optionally be sulphurized in an
amount up to 35% by weight. In an embodiment, the acid is a C4 to
C22 straight chain unsaturated monocarboxylic acid. The
monocarboxylic acid may be a sulphurized oleic acid. However, other
suitable materials are oleic acid itself, valeric acid and erucic
acid. A component of the anti-corrosion combination is a triazole
as previously defined. In an embodiment, the triazole is
tolylotriazole, which may be included in the compositions of the
disclosure include triazoles, thiazoles and certain diamine
compounds which are useful as metal deactivators or metal
passivators. Examples include triazole, benzotriazole and
substituted benzotriazoles, such as alkyl substituted derivatives.
The alkyl substituent may contain up to 1.5 carbon atoms, e.g. up
to 8 carbon atoms. The triazoles may contain other substituents on
the aromatic ring such as halogens, nitro, amino, mercapto, etc.
Examples of suitable compounds are benzotriazole and the
tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles,
octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles.
In a particular embodiment, the compound is benzotriazole and/or
tolyltriazole.
[0164] Illustrative substituents include, for example, alkyl that
is straight or branched chain, for example, methyl, ethyl,
n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl,
n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl; alkenyl that
is straight or branched chain, for example, prop-2-enyl,
but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2,4-dienyl,
dec-10-enyl or eicos-2-enyl; cycloalkyl that is, for example,
cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or
cyclododecyl; aralkyl that is, for example, benzyl, 2-phenylethyl,
benzhydryl or naphthylmethyl; aryl that is, for example, phenyl or
naphthyl; heterocyclic group that is, for example, a morpholine,
pyrrolidine, piperidine or a perhydroazepine ring; alkylene
moieties that include, for example, methylene, ethylene, 1:2- or
1:3-propylene, 1:4-butylene, 1:6-hexylene, 1:8-octylene,
1:10-decylene and 1:12-dodecylene.
[0165] Illustrative arylene moieties include, for example,
phenylene and naphthylene. 1-(or 4)-(dimethylaminomethyl) triazole,
1-(or 4)-(diethylaminomethyl) triazole, 1-(or
4)-(di-isopropylaminomethyl) triazole, 1-(or
4)-(di-n-butylaminomethyl) triazole, 1-(or
4)-(di-n-hexylaminomethyl) triazole, 1-(or
4)-(di-isooctylaminomethyl) triazole, 1-(or
4)-(di-(2-ethylhexyl)aminomethyl) triazole, 1-(or
4)-(di-n-decylaminomethyl) triazole, 1-(or
4)-(di-n-dodecylaminomethyl) triazole, 1-(or
4)-(di-n-octadecylaminomethyl) triazole, 1-(or
4)-(di-n-eicosylaminomethyl) triazole, 1-(or
4)-[di-(prop-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(but-2'-enyl)aminomethyl] triazole, 1-(or
4)-[di-(eicos-2'-enyl)aminomethyl] triazole, 1-(or
4)-(di-cyclohexylaminomethyl) triazole, 1-(or
4)-(di-benzylaminomethyl) triazole, 1-(or 4)-(di-phenylaminomethyl)
triazole, 1-(or 4)-(4'-morpholinomethyl) triazole, 1-(or
4)-(1'-pyrrolidinomethyl) triazole, 1-(or 4)-(1'-piperidinomethyl)
triazole, 1-(or 4)-(1'-perhydoroazepinomethyl) triazole, 1-(or
4)-(2',2''-dihydroxyethyl)aminomethyl]triazole, 1-(or
4)-(dibutoxypropyl-aminomethyl) triazole, 1-(or
4)-(dibutylthiopropyl-aminomethyl) triazole, 1-(or
4)-(di-butylaminopropyl-aminomethyl) triazole,
1-(or-4)-(1-methanomine)-N,N-bis(2-ethylhexyl)-methyl
benzotriazole, N,N-bis-(1- or 4-triazolylmethyl) laurylamine,
N,N-bis-(1- or 4-triazolylmethyl) oleylamine, N,N-bis-(1- or
4-triazolylmethyl) ethanolamine and N,N,N',N'-tetra(1- or
4-triazolylmethyl) ethylene diamine.
[0166] The metal deactivating agents which can be used in the
composition of the present disclosure includes, for example,
benzotriazole and the 4-alkylbenzotriazoles such as
4-methylbenzotriazole and 4-ethylbenzotriazole;
5-alkylbenzotriazoles such as 5-methylbenzotriazole,
5-ethylbenzotriazole; 1-alkylbenzotriazoles such as
1-dioctylauainomethyl-2,3-benzotriazole; benzotriazole derivatives
such as the 1-alkyltolutriazoles, for example,
1-dioctylaminomethyl-2,3-t-olutriazole; benzimidazole and
benzimidazole derivatives such as 2-(alkyldithio)-benzimidazoles,
for example, such as 2-(octyldithio)-benzimidazole,
2-(decyldithio)benzimidazole and 2-(dodecyldithio)-benzimidazole;
2-(alkyldithio)-toluimidazoles such as
2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole and
2-(dodecyldithio)-toluimidazole; indazole and indazole derivatives
of toluimidazoles such as 4-alkylindazole, 5-alkylindazole;
benzothiazole, 2-mercaptobenzothiazole derivatives (manufactured by
the Chiyoda Kagaku Co. under the trade designation "Thiolite
B-3100") and 2-(alkyldithio)benzothiazoles such as
2-(hexyldithio)benzothiazole and 2-(octyldithio)benzothiazole;
2-(alkyl-dithio)toluthiazoles such as 2-(benzyldithio)toluthiazole
and 2-(octyldithio)toluthiazole,
2-(N,N-dialkyldithiocarbamyl)benzothiazoles such as
2-(N,N-diethyldithiocarbamyl)benzothiazole,
2-(N,N-dibutyldithiocarbamyl)-benzotriazole and
2-N,N-dihexyl-dithiocarbamyl)benzotriazole; benzothiazole
derivatives of 2-(N,N-dialkyldithiocarbamyl)toluthiazoles such as
2-(N,N-diethyldithiocarbamyl)toluthiazole,
2-(N,N-dibutyldithiocarbamyl)toluthiazole,
2-(N,N-dihexyl-dithiocarbamyl)-toluthiazole;
2-(alkyldithio)benzoxazoles such as 2-(octyldithio)benzoxazole,
2-(decyldithio)-benzoxazole and 2-(dodecyldithio)benzoxazole;
benzoxazole derivatives of 2-(alkyldithio)toluoxazoles such as
2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole,
2-(dodecyldithio)toluoxazole;
2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as
2,5-bis(heptyldithio)-1,3,4-thiadiazole,
2,5-bis-(nonyldithio)-1,-3,4-thiadiazole,
2,5-bis(dodecyldithio)-1,3,4-thiadiazole and
2,5-bis-(octadecyldithio)-1,3,4-thiadiazole;
2,5-bis(N,N-dialkyl-dithiocarbamyl)-1,3,4-thiadiazoles such as
2,5-bis(N,N-diethyldithiocarbamyl)-1,3,-4-thiadiazole,
2,5-bis(N,N-dibutyldithiocarbamyl)-1,3,4-thiadiazole and
2,5-bis(N,N-dioctyldithiocarbamyl) 1,3,4-thiadiazole; thiadiazole
derivatives of
2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazoles such as
2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole and
2-N,N-dioctyl-dithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and
triazole derivatives of 1-alkyl-2,4-triazoles such as
1-dioctylaminomethyl-2,4-triazole; or concentrates and/or mixtures
thereof.
[0167] Although their presence is not required to obtain the
benefit of the present disclosure, the metal deactivator(s) and
corrosion inhibitor(s) may be present from zero to about 1% by
weight (e.g. from 0.01% to about 0.5% by weight) of the total
composition of the present disclosure.
[0168] Antiwear Additive(s) or Inhibitor(s).
[0169] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, 4, 5, or 6, or more) antiwear additive or wear inhibitor.
Any antiwear additive that is known or that becomes known may be
utilized in the lubricating of the present disclosure. The antiwear
additive may be an alkyldithiophosphate(s), aryl phosphate(s)
and/or phosphite(s). The antiwear additive(s) may be essentially
free of metals, or they may contain metal salts.
[0170] In certain embodiments, the antiwear additive is a phosphate
ester or salt thereof. A phosphate ester or salt may be a
monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphate,
wherein each hydrocarbyl group is saturated. In an embodiment, each
hydrocarbyl group independently contains from about 8 to about 30,
or from about 12 up to about 28, or from about 14 up to about 24,
or from about 14 up to about 18 carbons atoms. In an embodiment,
the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl
groups include at least one of tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl groups, and mixtures thereof.
[0171] A phosphate ester or salt is a phosphorus acid ester
prepared by reacting at least one (e.g., 1, 2, 3, 4, or more)
phosphorus acid or anhydride with a saturated alcohol. The
phosphorus acid or anhydride cam be an inorganic phosphorus
reagent, such as phosphorus pentoxide, phosphorus trioxide,
phosphorus tetroxide, phosphorous acid, phosphoric acid, phosphorus
halide, lower phosphorus esters, or a phosphorus sulfide, including
phosphorus pentasulfide, and the like. Lower phosphorus acid esters
may contain from 1 to about 7 carbon atoms in each ester group.
Alcohols used to prepare the phosphorus acid esters or salts.
Examples of commercially available alcohols and alcohol mixtures
include Alfol 1218 (a mixture of synthetic, primary, straight-chain
alcohols containing 12 to 18 carbon atoms); Alfol 20+ alcohols
(mixtures of C18-C28 primary alcohols having mostly C20 alcohols as
determined by GLC (gas-liquid-chromatography)); and Alfol22+
alcohols (C18-C28 primary alcohols containing primarily C22
alcohols). Alfol alcohols are available from, e.g., Continental Oil
Company. Another example of a commercially available alcohol
mixture is Adol 60 (about 75% by weight of a straight chain C22
primary alcohol, about 15% of a C20 primary alcohol, and about 8%
of C18 and C24 alcohols). The Adol alcohols are marketed by Ashland
Chemical.
[0172] The antiwear additive may include at least one (e.g., a
mixture of) monohydric fatty alcohol. For example, a mixture of
monohydric fatty alcohols derived from naturally occurring
triglycerides and ranging in chain length from C8 to C18 may be
utilized as an antiwear additive. A variety of monohydric fatty
alcohol mixtures are available from Procter & Gamble Company.
These mixtures contain various amounts of fatty alcohols containing
12, 14, 16, or 18 carbon atoms. For example, CO-1214 is a fatty
alcohol mixture containing 0.5% of C10 alcohol, 66.0% of C12
alcohol, 26.0% of C14 alcohol and 6.5% of C16 alcohol.
[0173] Another group of commercially available alcohol mixtures
include the "Neodol" products available from Shell Chemical Co. For
example, Neodol 23 is a mixture of C12 and C13 alcohols; Neodol 25
is a mixture of C12 to C15 alcohols; and Neodol 45 is a mixture of
C14 to C15 linear alcohols. The phosphate contains from about 14 to
about 18 carbon atoms in each hydrocarbyl group. The hydrocarbyl
groups of the phosphate may be derived from a mixture of fatty
alcohols having from about 14 up to about 18 carbon atoms. The
hydrocarbyl phosphate may also be derived from a fatty vicinal
diol. Fatty vicinal diols include, but not limited to, those
available from Ashland Oil under the general trade designation Adol
114 and Adol 158. The former is derived from a straight chain alpha
olefin fraction of C11-C14, and the latter is derived from a
C15-C18 fraction.
[0174] Phosphate salts may be prepared by reacting an acidic
phosphate ester with an amine compound or a metallic base to form
an amine or a metal salt. The amines may be monoamines or
polyamines. Useful amines include those amines disclosed in U.S.
Pat. No. 4,234,435.
[0175] Illustrative monoamines may contain a hydrocarbyl group,
which contains from 1 to about 30 carbon atoms, or from 1 to about
12, or from 1 to about 6. Examples of primary monoamines useful in
the present disclosure include methylamine, ethylamine,
propylamine, butylamine, cyclopentylamine, cyclohexylamine,
octylamine, dodecylamine, allylamine, cocoamine, stearylamine, and
laurylamine. Examples of secondary monoamines include
dimethylamine, diethylamine, dipropylamine, dibutylamine,
dicyclopentylamine, dicyclohexylamine, methylbutylamine,
ethylhexylamine, etc.
[0176] An amine may be a fatty (C8-C30) amine which includes
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,
n-hexadecylamine, n-octadecylamine, oleyamine, etc. Also useful
fatty amines include commercially available fatty amines, such as
"Armeen" amines (products available from Akzo Chemicals, Chicago,
Ill.), e.g. Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT,
Armeen S and Armeen SD, wherein the letter designation relates to
the fatty group, such as coco, oleyl, tallow, or stearyl
groups.
[0177] Other useful amines include primary ether amines, such as
those represented by the formula:
R''(OR')xNH.sub.2,
wherein:
[0178] R' is a divalent alkylene group having about 2 to about 6
carbon atoms;
[0179] x is a number from one to about 150, or from about one to
about five, or one; and
[0180] R'' is a hydrocarbyl group of about 5 to about 150 carbon
atoms.
[0181] An exemplary or illustrative ether amine is available under
the name SURFAM.RTM. amines produced and marketed by Mars Chemical
Company, Atlanta, Ga. Additional exemplary ether amines include
those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A
(linear C16), and SURFAM P17B (tridecyloxypropylamine). The carbon
chain lengths (i.e., C14, etc.) of the SURFAM ether amines
described above and used hereinafter are approximate and include
the oxygen ether linkage.
[0182] A further illustrative amine is a tertiary-aliphatic primary
amine. For example, the aliphatic group, such as an alkyl group,
contains from about 4 to about 30, or from about 6 to about 24, or
from about 8 to about 22 carbon atoms. Usually the tertiary alkyl
primary amines are monoamines the alkyl group is a hydrocarbyl
group containing from one to about 27 carbon atoms. Such amines are
illustrated by tert-butylamine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, tert-octacosanylamine,
and combinations thereof. Mixtures of tertiary aliphatic amines may
also be used in preparing the phosphate salt. Illustrative of amine
mixtures of this type are "Primene 81R", which is a mixture of
C11-C14 tertiary alkyl primary amines, and "Primene JMT", which is
a similar mixture of C18-C22 tertiary alkyl primary amines (both
are available from Rohm and Haas Company). The tertiary aliphatic
primary amines and methods for their preparation are known to those
of ordinary skill in the art.
[0183] Another illustrative amine is a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines,
tetra- and dihydropyridines, pyrroles, indoles, piperidines,
imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles,
purines, morpholines, thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkyl-piperazines,
N,N'-diaminoalkylpiperazines, azepines, azocines, azonines,
azecines and tetra-, di- and perhydro derivatives of each of the
above, and mixtures of two or more (e.g., 2, 3, 4, 5, 6, or more)
of these heterocyclic amines. In certain embodiments, the
heterocyclic amines are saturated 5- and 6-membered heterocyclic
amines containing only nitrogen, oxygen and/or sulfur in the hetero
ring, especially the piperidines, piperazines, thiomorpholines,
morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl
substituted piperidines, piperazine, aminoalkyl substituted
piperazines, morpholine, aminoalkyl substituted morpholines,
pyrrolidine, and aminoalkyl-substituted pyrrolidines, are
especially preferred. Usually the aminoalkyl substituents are
substituted on a nitrogen atom forming part of the hetero ring.
Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are
also useful. Examples include N-(2-hydroxyethyl)cyclohexylamine,
3-hydroxycyclopentylamine, parahydroxyaniline,
N-hydroxyethylpiperazine, and the like.
[0184] The metal salts of the phosphorus acid esters may be
prepared by the reaction of a metal base with the acidic phosphorus
ester. The metal base may be any metal compound capable of forming
a metal salt. Examples of metal bases include metal oxides,
hydroxides, carbonates, sulfates, borates, or the like. The metals
of the metal base include Group IA, IIA, IB through VIIB, and VIII
metals (CAS version of the Periodic Table of the Elements). These
metals include the alkali metals, alkaline earth metals and
transition metals. In an embodiment, the metal is a Group IIA
metal, such as calcium or magnesium, Group IIB metal, such as zinc,
or a Group VIIB metal, such as manganese. In particular
embodiments, the metal is magnesium, calcium, manganese or zinc.
Examples of metal compounds which may be reacted with the
phosphorus acid include zinc hydroxide, zinc oxide, copper
hydroxide, copper oxide, etc.
[0185] The composition of the present disclosure also may include a
fatty imidazoline or a reaction product of a fatty carboxylic acid
and at least one polyamine. The fatty imidazoline has fatty
substituents containing from 8 to about 30, or from about 12 to
about 24 carbon atoms. The substituent may be saturated or
unsaturated, for example, heptadeceneyl derived olyel groups. In a
particular embodiment, the substituents are saturated. In one
aspect, the fatty imidazoline may be prepared by reacting a fatty
carboxylic acid with a polyalkylenepolyamine. The fatty carboxylic
acids are can be mixtures of straight and branched chain fatty
carboxylic acids containing about 8 to about 30 carbon atoms, or
from about 12 to about 24, or from about 16 to about 18. Carboxylic
acids include the polycarboxylic acids or carboxylic acids or
anhydrides having from 2 to about 4 carbonyl groups, (e.g. 2
carbonyl groups). The polycarboxylic acids include succinic acids
and anhydrides and Diels-Alder reaction products of unsaturated
monocarboxylic acids with unsaturated carboxylic acids (such as
acrylic, methacrylic, maleic, fumaric, crotonic and itaconic
acids). In particular embodiments, the fatty carboxylic acids are
fatty monocarboxylic acids, having from about 8 to about 30, (e.g.
about 12 to about 24 carbon atoms), such as octanoic, oleic,
stearic, linoleic, dodecanoic, and tall oil acids. In an
embodiment, the fatty carboxylic acid is stearic acid. The fatty
carboxylic acid or acids are reacted with at least one polyamine.
The polyamines may be aliphatic, cycloaliphatic, heterocyclic or
aromatic. Examples of the polyamines include alkylene polyamines
and heterocyclic polyamines.
[0186] The antiwear additive according to the present disclosure
has very high effectiveness when used in low concentrations and is
free of chlorine. For the neutralization of the phosphoric esters,
the latter are taken and the corresponding amine slowly added with
stirring. The resulting heat of neutralization is removed by
cooling. The antiwear additive according to the present disclosure
can be incorporated into the respective base liquid with the aid of
fatty substances (e.g., tall oil fatty acid, oleic acid, etc.) as
solubilizers. The base liquids used are napthenic or paraffinic
base oils, synthetic oils (e.g., polyglycols, mixed polyglycols),
polyolefins, carboxylic esters, etc.
[0187] In further embodiments, the compositions of the present
disclosure can contain at least one phosphorus containing antiwear
additive. Examples of such additives are amine phosphate antiwear
additives such as that known under the trade name IRGALUBE 349
and/or triphenyl phosphorothionate antiwear additives, such as that
known under the trade name IRGALUBE TPPT. Such amine phosphates may
be present in an amount of from about 0.01 to about 2% (e.g. about
0.2 to about 1.5%) by weight of the lubricant composition, while
such phosphorothionates are suitably present in an amount of from
about 0.01 to about 3% (e.g., about 0.5 to about 1.5%) by weight of
the composition of the present disclosure. A mixture of an amine
phosphate and phosphorothionate may be employed.
[0188] Neutral organic phosphates may be present in an amount from
zero to about 4% (e.g., about 0.1 to about 2.5%) by weight of the
composition of the present disclosure. The above amine phosphates
can be mixed together to form a single component capable of
delivering antiwear performance. The neutral organic phosphate is
also a conventional ingredient of lubricating oils.
[0189] Phosphates for use in the present disclosure include
phosphates, acid phosphates, phosphites, and acid phosphites. The
phosphates include triaryl phosphates, trialkyl phosphates,
trialkylaryl phosphates, triarylalkyl phosphates, trialkenyl
phosphates, or combinations thereof. As specific examples of these,
referred to are triphenyl phosphate, tricresyl phosphate,
benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl
phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate,
dicresylphenyl phosphate, ethylphenyldiphenyl phosphate,
diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate,
dipropylphenylphenyl phosphate, triethylphenyl phosphate,
tripropylphenyl phosphate, butylphenyldiphenyl phosphate,
dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexyl
phosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphate,
trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate,
tristearyl phosphate, trioleyl phosphate, or combinations
thereof.
[0190] The acid phosphates include, for example, 2-ethylhexyl acid
phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid
phosphate, tetracosyl acid phosphate, isodecyl acid phosphate,
lauryl acid phosphate, tridecyl acid phosphate, stearyl acid
phosphate, isostearyl acid phosphate, or combinations thereof.
[0191] The phosphites include, for example, triethyl phosphite,
tributyl phosphite, triphenyl phosphite, tricresyl phosphite,
tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl
phosphite, trilauryl phosphite, triisooctyl phosphite,
diphenylisodecyl phosphite, tristearyl phosphite, trioleyl
phosphite, or combinations thereof.
[0192] The acid phosphites include, for example, dibutyl
hydrogenphosphite, dilauryl hydrogenphosphite, dioleyl
hydrogenphosphite, distearyl hydrogenphosphite, diphenyl
hydrogenphosphite, or combinations thereof.
[0193] Amines that form amine salts with such phosphates include,
for example, mono-substituted amines, di-substituted amines and
tri-substituted amines. Examples of the mono-substituted amines
include butylamine, pentylamine, hexylamine, cyclohexylamine,
octylamine, laurylamine, stearylamine, oleylamine and benzylamine;
and those of the di-substituted amines include dibutylamine,
dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine,
dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl
monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine,
benzyl monoethanolamine, phenyl monoethanolamine, and tolyl
monopropanolamine. Examples of tri-substituted amines include
tributylamine, tripentylamine, trihexylamine, tricyclohexylamine,
trioctylamine, trilaurylamine, tristearylamine, trioleylamine,
tribenzylamine, dioleyl monoethanolamine, dilauryl
monopropanolamine, dioctyl monoethanolamine, dihexyl
monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine,
stearyl dipropanolamine, lauryl diethanolamine, octyl
dipropanolamine, butyl diethanolamine, benzyl diethanolamine,
phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine,
triethanolamine, and tripropanolamine. Phosphates or their amine
salts are added to the base oil in an amount from zero to about 5%
by weight, (e.g. from about 0.1 to about 2% by weight) relative to
the total weight of the composition of the present disclosure.
[0194] Illustrative carboxylic acids to be reacted with amines
include, for example, aliphatic carboxylic acids, dicarboxylic
acids (dibasic acids), aromatic carboxylic acids, or combinations
thereof. The aliphatic carboxylic acids have from 8 to 30 carbon
atoms, and may be saturated or unsaturated, and linear or branched.
Specific examples of the aliphatic carboxylic acids include
pelargonic acid, lauric acid, tridecanoic acid, myristic acid,
palmitic acid, stearic acid, isostearic acid, eicosanoic acid,
behenic acid, triacontanoic acid, caproleic acid, undecylenic acid,
oleic acid, linolenic acid, erucic acid, linoleic acid, or
combinations thereof. Specific examples of the dicarboxylic acids
include octadecylsuccinic acid, octadecenylsuccinic acid, adipic
acid, azelaic acid, sebacic acid, or combinations thereof. One
example of the aromatic carboxylic acids is salicylic acid.
Illustrative amines to be reacted with carboxylic acids include,
for example, polyalkylene-polyamines, such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, hexaethyleneheptamine,
heptaethyleneoctamine, dipropylenetriamine,
tetrapropylenepentamine, hexabutyleneheptamine, or combinations
thereof; and alkanolamines, such as monoethanolamine and
diethanolamine. Of these, preferred are a combination of isostearic
acid, tetraethylenepentamine, or combinations thereof; and a
combination of oleic acid and diethanolamine. Reaction products of
carboxylic acids and amines may be added to the base oil in an
amount of from zero to about 5% by weight (e.g. from about 0.03 to
about 3% by weight) relative to the total weight of the composition
of the present disclosure.
[0195] Other illustrative antiwear additives include phosphites,
thiophosphites, phosphates, and thiophosphates, including mixed
materials having, for instance, one or two sulfur atoms, i.e.,
monothio- or dithio compounds. As used herein, the term
"hydrocarbyl substituent" or "hydrocarbyl group" is used in its
ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers to a group primarily composed of carbon and
hydrogen atoms and is attached to the remainder of the molecule
through a carbon atom and does not exclude the presence of other
atoms or groups in a proportion insufficient to detract from the
molecule having a predominantly hydrocarbon character. In general,
no more than two, preferably no more than one, non-hydrocarbon
substituent will be present for every ten carbon atoms in the
hydrocarbyl group; typically, there will be no non-hydrocarbon
substituents in the hydrocarbyl group. A more detailed definition
of the terms "hydrocarbyl substituent" or "hydrocarbyl group," is
described in U.S. Pat. No. 6,583,092.
[0196] Specific examples of some phosphites and thiophosphites
within the scope of the disclosure include phosphorous acid, mono-,
di- or tri-thiophosphorous acid, mono-, di- or tri-propyl phosphite
or mono-, di- or tri-thiophosphite; mono-, di- or tri-butyl
phosphite or mono-, di- or tri-thiophosphite; mono-, di- or
tri-amyl phosphite or mono-, di- or tri-thiophosphite; mono-, di-
or tri-hexyl phosphite; or mono-, di- or tri-thiophosphite; mono-,
di- or tri-phenyl phosphite; or mono-, di- or tri-thiophosphite;
mono-, di- or tri-tolyl phosphite; or mono-, di- or
tri-thiophosphite; mono-, di- or tri-cresyl phosphite; or mono-,
di- or tri-thiophosphite; dibutyl phenyl phosphite; or mono-, di-
or tri-phosphite; amyl dicresyl phosphite; or mono-, di- or
tri-thiophosphite, and any of the above with substituted groups,
such as chlorophenyl or chlorobutyl.
[0197] Specific examples of the phosphates and thiophosphates
within the scope of the disclosure include phosphoric acid, mono-,
di-, or tri-thiophosphoric acid, mono-, di-, or tri-propyl
phosphate or mono-, di-, or tri-thiophosphate; mono-, di-, or
tri-butyl phosphate or mono-, di-, or tri-thiophosphate; mono-,
di-, or tri-amyl phosphate or mono-, di-, or tri-thiophosphate;
mono-, di-, or tri-hexyl phosphate or mono-, di-, or
tri-thiophosphate; mono-, di-, or tri-phenyl phosphate or mono-,
di-, or tri-thiophosphate; mono-, di-, or tritolyl phosphate or
mono-, di-, or trithiophosphate; mono-, di-, or tri-cresyl
phosphate or mono-, di-, or tri-thiophosphate; dibutyl phenyl
phosphate or mono-, di-, or tri-phosphate, amyl dicresyl phosphate
or mono-, di-, or tri-thiophosphate, and any of the above with
substituted groups, such as chlorophenyl or chlorobutyl.
[0198] These phosphorus compounds may be prepared by well-known
reactions. For example, the reaction of an alcohol or a phenol with
phosphorus trichloride or by a transesterification reaction.
Alcohols and phenols can be reacted with phosphorus pentoxide to
provide a mixture of an alkyl or aryl phosphoric acid and a dialkyl
or diaryl phosphoric acid. Alkyl phosphates can also be prepared by
the oxidation of the corresponding phosphites. Thiophosphates can
be prepared by the reaction of phosphites with elemental sulfur. In
any case, the reaction can be conducted with moderate heating.
Moreover, various phosphorus esters can be prepared by reaction
using other phosphorus esters as starting materials. Thus, medium
chain (C9 to C22) phosphorus esters have been prepared by reaction
of dimethylphosphite with a mixture of medium-chain alcohols by
means of a thermal transesterification or an acid- or
base-catalyzed transesterification. See, for example, U.S. Pat. No.
4,652,416. Most such materials are also commercially available; for
instance, triphenyl phosphite is available from Albright and Wilson
as Duraphos TPP.TM.; di-n-butyl hydrogen phosphite from Albright
and Wilson as Duraphos DBHP.TM.; and triphenylthiophosphate from
Ciba Specialty Chemicals as Irgalube TPPT.TM..
[0199] Examples of esters of the dialkylphosphorodithioic acids
include esters obtained by reaction of the dialkyl
phosphorodithioic acid with an alpha, beta-unsaturated carboxylic
acid (e.g., methyl acrylate) and, optionally an alkylene oxide such
as propylene oxide.
[0200] One or more of the above-identified metal dithiophosphates
may be used from about zero to about 2% by weight (e.g., from about
0.1 to about 1% by weight) based on the weight of the total
composition.
[0201] The hydrocarbyl in the dithiophosphate may be alkyl,
cycloalkyl, aralkyl or alkaryl groups, or a substantially
hydrocarbon group of similar structure. Illustrative alkyl groups
include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl
groups, n-hexyl, methylisobutyl, heptyl, 2-ethylhexyl, diisobutyl,
isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
Illustrative lower alkylphenyl groups include butylphenyl,
amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewise are
useful and these include chiefly cyclohexyl and the lower
alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may
also be used, e.g., chloropentyl, dichlorophenyl, and
dichlorodecyl.
[0202] The phosphorodithioic acids from which the metal salts
useful in this disclosure are prepared are well known. Examples of
dihydrocarbylphosphorodithioic acids and metal salts, and processes
for preparing such acids and salts are found in, for example U.S.
Pat. Nos. 4,263,150; 4,289,635; 4,308,154; and 4,417,990. These
patents are hereby incorporated by reference.
[0203] The phosphorodithioic acids may be prepared by the reaction
of a phosphorus sulfide with an alcohol or phenol or mixtures of
alcohols. An exemplary reaction involves four moles of the alcohol
or phenol and one mole of phosphorus pentasulfide, and may be
carried out within the temperature range from about 50.degree. C.
to about 200.degree. C. Thus, the preparation of O,O-di-n-hexyl
phosphorodithioic acid involves the reaction of a mole of
phosphorus pentasulfide with four moles of n-hexyl alcohol at about
100.degree. C. for about two hours. Hydrogen sulfide is liberated
and the residue is the desired acid. The preparation of the metal
salts of these acids may be effected by reaction with metal
compounds as well known in the art.
[0204] The metal salts of dihydrocarbyldithiophosphates, which are
useful in the present disclosure, include those salts containing
Group I metals, Group II metals, aluminum, lead, tin, molybdenum,
manganese, cobalt, and nickel. The Group II metals, aluminum, tin,
iron, cobalt, lead, molybdenum, manganese, nickel and copper are
among the preferred metals. Zinc and copper are especially useful
metals. Examples of metal compounds which may be reacted with the
acid include lithium oxide, lithium hydroxide, sodium hydroxide,
sodium carbonate, potassium hydroxide, potassium carbonate, silver
oxide, magnesium oxide, magnesium hydroxide, calcium oxide, zinc
hydroxide, strontium hydroxide, cadmium oxide, cadmium hydroxide,
barium oxide, aluminum oxide, iron carbonate, copper hydroxide,
lead hydroxide, tin butylate, cobalt hydroxide, nickel hydroxide,
nickel carbonate, and the like.
[0205] In some instances, the incorporation of certain ingredients
such as small amounts of the metal acetate or acetic acid in
conjunction with the metal reactant will facilitate the reaction
and result in an improved product. For example, the use of up to
about 5% of zinc acetate in combination with the required amount of
zinc oxide facilitates the formation of a zinc phosphorodithioate
with potentially improved performance properties.
[0206] Especially useful metal phosphorodithloates can be prepared
from phosphorodithloic acids, which in turn are prepared by the
reaction of phosphorus pentasulfide with mixtures of alcohols. In
addition, the use of such mixtures enables the utilization of less
expensive alcohols, which individually may not yield oil-soluble
phosphorodithioic acids. Thus, a mixture of isopropyl and
hexylalcohols can be used to produce a very effective, oil-soluble
metal phosphorodithioate. For the same reason mixtures of
phosphorodithioic acids can be reacted with the metal compounds to
form less expensive, oil-soluble salts.
[0207] The mixtures of alcohols may be mixtures of different
primary alcohols, mixtures of different secondary alcohols, or
mixtures of primary and secondary alcohols. Examples of useful
mixtures include: n-butanol and n-octanol; n-pentanol and
2-ethyl-1-hexanol; isobutanol and n-hexanol; isobutanol and isoamyl
alcohol; isopropanol and 2-methyl-4-pentanol; isopropanol and
sec-butyl alcohol; isopropanol and isooctyl alcohol; and the
like.
[0208] Organic triesters of phosphorus acids are also employed in
lubricants. Exemplary esters include triarylphosphates, trialkyl
phosphates, neutral alkylaryl phosphates, alkoxyalkyl phosphates,
triaryl phosphite, trialkylphosphite, neutral alkyl aryl
phosphites, neutral phosphonate esters and neutral phosphine oxide
esters. In one embodiment, the long chain dialkyl phosphonate
esters are used. For example, the dimethyl-, diethyl-, and/or
dipropyl-oleyl phosphonates can be used. Neutral acids of
phosphorus acids are the triesters rather than an acid (HO-P) or a
salt of an acid.
[0209] Any C4 to C8 alkyl or higher phosphate ester may be employed
in the disclosure. For example, tributyl phosphate (TBP) and tri
isooctal phosphate (TOF) can be used. The specific triphosphate
ester or combination of esters can easily be selected by one
skilled in the art to adjust the density, viscosity, etc., of the
formulated fluid. Mixed esters, such as dibutyl octyl phosphate or
the like may be employed rather than a mixture of two or more
trialkyl phosphates.
[0210] A trialkyl phosphate is often useful to adjust the specific
gravity of the formulation, but it is desirable that the specific
trialkyl phosphate be a liquid at low temperatures. Consequently, a
mixed ester containing at least one partially alkylated with a C3
to C4 alkyl group is very desirable, for example, 4-isopropylphenyl
diphenyl phosphate or 3-butylphenyl diphenyl phosphate. Even more
desirable is a triaryl phosphate produced by partially alkylating
phenol with butylene or propylene to form a mixed phenol which is
then reacted with phosphorus oxychloride as taught in U.S. Pat. No.
3,576,923.
[0211] Any mixed triaryl phosphate (TAP) esters may be used as
cresyl diphenyl phosphate, tricresyl phosphate, mixed xylyl cresyl
phosphates, lower alkylphenyl/phenyl phosphates, such as mixed
isopropylphenyl/phenyl phosphates, t-butylphenyl phenyl phosphates.
These esters are used extensively as plasticizers, functional
fluids, gasoline additives, flame-retardant additives and the
like.
[0212] A metal alkylthiophosphate and more particularly a metal
dialkyl dithio phosphate in which the metal constituent is zinc, or
zinc dialkyl dithio phosphate (ZDDP) can be a useful component of
the lubricating oils of this disclosure. ZDDP can be derived from
primary alcohols, secondary alcohols or mixtures thereof. ZDDP
compounds are of the formula:
Zn[SP(S)(OR1)(OR2)].sub.2,
wherein R1 and R2 are C1-C18 alkyl groups (e.g. C2-C12 alkyl
groups).
[0213] These alkyl groups may be straight chain or branched.
Alcohols used in the ZDDP can be propanol, 2-propanol, butanol,
secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol,
n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the
like. Mixtures of secondary alcohols or of primary and secondary
alcohol can be utilized. Alkyl aryl groups may also be used.
[0214] Exemplary zinc dithiophosphates that 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".
[0215] ZDDP may be used in amounts of from about zero to about 3
weight percent (e.g. from about 0.05 weight percent to about 2
weight percent, from about 0.1 weight percent to about 1.5 weight
percent, or from about 0.1 weight percent to about 1 weight
percent) based on the total weight of the composition for the
present disclosure, although more or less can often be used
advantageously. A secondary ZDDP may be present in an amount of
from zero to about 1 weight percent of the total weight of the
composition for the present disclosure.
[0216] Extreme Pressure Agent(s).
[0217] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, or 4, or more) extreme pressure agent. Any extreme
pressure agent that is known or that becomes know may be utilized
in the composition of the present disclosure.
[0218] The extreme pressure agents can be at least one sulfur-based
extreme pressure agents, such as sulfides, sulfoxides, sulfones,
thiophosphinates, thiocarbonates, sulfurized fats and oils,
sulfurized olefins, the like, or combinations thereof; at least one
phosphorus-based extreme pressure agents, such as phosphoric acid
esters (e.g., tricresyl phosphate (TCP) and the like), phosphorous
acid esters, phosphoric acid ester amine salts, phosphorous acid
ester amine salts, the like, or combinations thereof; halogen-based
extreme pressure agents, such as chlorinated hydrocarbons, the
like, or combinations thereof; organometallic extreme pressure
agents, such as thiophosphoric acid salts (e.g., zinc
dithiophosphate (ZnDTP) and the like), thiocarbamic acid salts, or
combinations thereof; and the like.
[0219] The phosphoric acid ester, thiophosphoric acid ester, and
amine salts thereof functions to enhance the lubricating
performances, and can be selected from known compounds
conventionally employed as extreme pressure agents. For example,
phosphoric acid esters, a thiophosphoric acid ester, or an amine
salt thereof which has an alkyl group, an alkenyl group, an
alkylaryl group, or an aralkyl group, any of which contains
approximately 3 to 30 carbon atoms, may be employed.
[0220] Examples of the phosphoric acid esters include aliphatic
phosphoric acid esters such as triisopropyl phosphate, tributyl
phosphate, ethyl dibutyl phosphate, trihexyl phosphate,
tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl
phosphate, and trioleyl phosphate; and aromatic phosphoric acid
esters such as benzyl phenyl phosphate, allyl diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate,
cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl
diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl
diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl
phosphate, tripropylphenyl phosphate, butylphenyl diphenyl
phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl
phosphate. In an embodiment, the phosphoric acid ester is a
trialkylphenyl phosphate.
[0221] Examples of the thiophosphoric acid esters include aliphatic
thiophosphoric acid esters such as triisopropyl thiophosphate,
tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl
thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl
thiophosphate, tristearyl thiophosphate, and trioleyl
thiophosphate; and aromatic thiophosphoric acid esters such as
benzyl phenyl thiophosphate, allyl diphenyl thiophosphate,
triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl
thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl
thiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl
phenyl thiophosphate, propylphenyl diphenyl thiophosphate,
dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate,
tripropylphenyl thiophosphate, butylphenyl diphenyl thiophosphate,
dibutylphenyl phenyl thiophosphate, and tributylphenyl
thiophosphate. In an embodiment, the thiophosphoric acid ester is a
trialkylphenyl thiophosphate.
[0222] Also employable are amine salts of the above-mentioned
phosphates and thiophosphates. Amine salts of acidic alkyl or aryl
esters of the phosphoric acid and thiophosphoric acid are also
employable. In an embodiment, the amine salt is an amine salt of
trialkylphenyl phosphate or an amine salt of alkyl phosphate.
[0223] One or any combination of the compounds selected from the
group consisting of a phosphoric acid ester, a thiophosphoric acid
ester, and an amine salt thereof may be used.
[0224] The phosphorus acid ester and/or its amine salt function to
enhance the lubricating performance of the composition, and can be
selected from known compounds conventionally employed as extreme
pressure agents. For example, the extreme pressure agent can be a
phosphorus acid ester or an amine salt thereof, which has an alkyl
group, an alkenyl group, an alkylaryl group, or an aralkyl group,
any of which contains approximately 3 to 30 carbon atoms.
[0225] Examples of phosphorus acid esters that may be used includes
aliphatic phosphorus acid esters, such as triisopropyl phosphite,
tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite,
tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl
phosphite, and trioleyl phosphite; and aromatic phosphorus acid
esters such as benzyl phenyl phosphite, allyl diphenylphosphite,
triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite,
tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl
phosphite, dicresyl phenyl phosphite, ethylphenyl diphenyl
phosphite, diethylphenyl phenyl phosphite, propylphenyl diphenyl
phosphite, dipropylphenyl phenyl phosphite, triethylphenyl
phosphite, tripropylphenyl phosphite, butylphenyl diphenyl
phosphite, dibutylphenyl phenyl phosphite, and tributylphenyl
phosphite. Also favorably employed are dilauryl phosphite, dioleyl
phosphite, dialkyl phosphites, and diphenyl phosphite. In certain
embodiments, the phosphorus acid ester is a dialkyl phosphite or a
trialkyl phosphite.
[0226] The phosphate salt may be derived from a polyamine, such as
alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines,
hydroxy containing polyamines, condensed polyamines arylpolyamines,
and heterocyclic polyamines. Examples of these amines include
Ethoduomeen T/13 and T/20, which are ethylene oxide condensation
products of N-tallowtrimethylenediamine containing 3 and 10 moles
of ethylene oxide per mole of diamine, respectively.
[0227] In another embodiment, the polyamine is a fatty diamine. The
fatty diamine may include mono- or dialkyl, symmetrical or
asymmetrical ethylene diamines, propane diamines (1,2 or 1,3), and
polyamine analogs of the above. Suitable commercial fatty
polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S
(N-soya-1,3-diaminopropane), Duomeen T
(N-tallow-1,3-diaminopropane), and Duomeen O
(N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available
from Armak Chemical Co., Chicago, Ill.
[0228] Such alkylenepolyamines include methylenepolyamines,
ethylenepolyamines, butylenepolyamines, propylenepolyamines,
pentylenepolyamines, etc. The higher homologs and related
heterocyclic amines, such as piperazines and N-amino
alkyl-substituted piperazines, are also included. Specific examples
of such polyamines are ethylenediamine, triethylenetetramine,
tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine, tetraethylenepentamine,
hexaethyleneheptamine, pentaethylenehexamine, etc. Higher homologs
obtained by condensing two or more of the above-noted
alkyleneamines are similarly useful as are mixtures of two or more
of the aforedescribed polyamines.
[0229] In one embodiment the polyamine is an ethylenepolyamine.
Such polyamines are described in detail under the heading Ethylene
Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd
Edition, Vol. 7, pages 22-37, Interscience Publishers, New York
(1965). Ethylenepolyamines can be a complex mixture of
polyalkylenepolyamines, including cyclic condensation products.
[0230] Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mixtures to leave,
as residue, what is often termed "polyamine bottoms". The
alkylenepolyamine bottoms can be characterized as having less than
2%, usually less than 1% (by weight) material boiling below about
200.degree. C. An exemplary sample of such ethylene polyamine
bottoms obtained from the Dow Chemical Company of Freeport, Tex.
designated "E-100". These alkylenepolyamine bottoms include cyclic
condensation products, such as piperazine, and higher analogs of
diethylenetriamine, triethylenetetramine and the like. These
alkylenepolyamine bottoms can be reacted solely with the acylating
agent or they can be used with other amines, polyamines, or
mixtures thereof. Another useful polyamine is a condensation
reaction between at least one hydroxy compound with at least one
polyamine reactant containing at least one primary or secondary
amino group. In an embodiment, the hydroxy compounds are alcohols
and amines. The polyhydric alcohols are described below. In one
embodiment, the hydroxy compounds are polyhydric amines. Polyhydric
amines include any of the above-described monoamines reacted with
an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene
oxide, etc.) having from two to about 20 carbon atoms, or from two
to about four. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1,3-propanediol,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and
N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine. IN an
embodiment, the polyhydric amin is tris(hydroxymethyl)aminomethane
(THAM).
[0231] Polyamines which react with the polyhydric alcohol or amine
to form the condensation products or condensed amines, are
described above. In an embodiment, the polyamine include at least
one of triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
pentaethylenehexamine (PEHA), and mixtures of polyamines, such as
the above-described "amine bottoms".
[0232] In some embodiments, the extreme pressure additive or
additives includes sulphur-based extreme pressure additives, such
as dialkyl sulphides, dibenzyl sulphide, dialkyl polysulphides,
dibenzyl disulphide, alkyl mercaptans, dibenzothiophene,
2,2'-dithiobis(benzothiazole), or combinations thereof;
phosphorus-based extreme pressure additives, such as trialkyl
phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl
phosphites, triaryl phosphites, dialkylhydrozine phosphites, or
combinations thereof; and/or phosphorus- and sulphur-based extreme
pressure additives, such as zinc dialkyldithiophosphates,
dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidic
thiophosphate esters, trialkyl trithiophosphates, or combinations
thereof. Extreme pressure additives can be used individually or in
the form of mixtures, conveniently in an amount within the range
from zero to about 2% by weight of the composition of the present
disclosure.
[0233] Dispersant(s).
[0234] In other embodiments, the composition of the present
disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more)
dispersant. During machine operation, oil-insoluble oxidation
byproducts are produced. The dispersant may be added to help keep
these byproducts in solution, thus diminishing their deposition on
metal surfaces. Any dispersant that is known or that becomes know
may be utilized in the composition of the present disclosure. The
dispersant may be present in an amount of .ltoreq.about 1.5 wt. %,
.ltoreq.about 1.25 wt. %, or .ltoreq.about 1 wt. %. For example,
the dispersant may be present in an amount of about 0.1 to about
1.5 wt. %, about 0.1 to about 1.25 wt. %, about 0.1 to about 1 wt.
%, about 0.1 to about 0.5 wt. %, about 0.25 to about 1.5 wt. %,
about 0.25 to about 1.25 wt. %, about 0.5 to about 1 wt. %, about
0.5 to about 1.5 wt. %, about 0.5 to about 1.25 wt. %, about 0.5 to
about 1 wt. %, about 0.75 to about 1.5 wt. %, about 0.75 to about
1.25 wt. %, or about 1 to about 1.5 wt. %.
[0235] In some embodiments, the dispersants is ashless or
ash-forming in nature. In an embodiment, the dispersant is an
ashless. So called ashless 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 form
ash upon combustion.
[0236] Suitable dispersants may contain a polar group attached to a
relatively high molecular weight hydrocarbon chain (e.g., about 50
to about 400 carbon atoms). In certain embodiments, the polar group
contains at least one element of nitrogen, oxygen, or
phosphorus.
[0237] A particularly useful class of dispersants are the
(poly)alkenylsuccinic derivatives, which may be produced by the
reaction of a long chain hydrocarbyl substituted succinic compound,
e.g. a hydrocarbyl substituted succinic anhydride, with a
polyhydroxy or polyamino compound. The long chain hydrocarbyl 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; 3,2145,707; 3,219,666;
3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904;
3,632,511; 3,787,374 and 4,234,435. 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.
[0238] Hydrocarbyl-substituted succinic acid and
hydrocarbyl-substituted succinic anhydride derivatives are useful
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound (e.g., a
hydrocarbon-substituted succinic acid compound having at least 50
carbon atoms in the hydrocarbon substituent) with at least one
equivalent of an alkylene amine are particularly useful.
[0239] Succinimides are formed by the condensation reaction between
hydrocarbyl substituted succinic anhydrides and amines. Molar
ratios can vary depending on the polyamine. For example, the molar
ratio of hydrocarbyl substituted succinic anhydride to TEPA can
vary from about 1:1 to about 5:1. Representative examples are shown
in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746;
3,322,670; and 3,652,616, 3,948,800; and Canada Patent No.
1,094,044.
[0240] Succinate esters may be formed by the condensation reaction
between hydrocarbyl substituted succinic anhydrides and alcohols or
polyols. Molar ratios can vary depending on the alcohol or polyol
used. For example, the condensation product of a hydrocarbyl
substituted succinic anhydride and pentaerythritol is a useful
dispersant.
[0241] Succinate ester amides may be formed by condensation
reaction between hydrocarbyl substituted 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. Representative
examples are shown in U.S. Pat. No. 4,426,305.
[0242] The molecular weight of the hydrocarbyl substituted succinic
anhydrides used in the preceding paragraphs can range between about
800 and about 2,500 or more. The above products can be post-reacted
with various reagents such as sulfur, oxygen, formaldehyde,
carboxylic acids, such as oleic acid. The above products can also
be post reacted with boron compounds, such as boric acid, borate
esters or highly borated dispersants, to form borated dispersants,
which may have from about 0.1 to about 5 moles of boron per mole of
dispersant reaction product.
[0243] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See U.S. Pat. No.
4,767,551, which is incorporated herein by reference. Process aids
and catalysts, such as oleic acid and sulfonic acids, can also be
part of the reaction mixture. Molecular weights of the alkylphenols
may range from about 800 to about 2,500. Representative examples
are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308;
3,751,365; 3,756,953; 3,798,165; and 3,803,039.
[0244] High molecular weight aliphatic acid modified Mannich
condensation products useful in this disclosure can be prepared
from high molecular weight alkyl-substituted hydroxyaromatics or
HNR.sub.2 group-containing reactants, wherein each R is
independently selected from hydrogen, C1-C18 alkyl, aryl, alkenyl,
alkaryl group.
[0245] Hydrocarbyl substituted amine ashless dispersant additives
are well known to one skilled in the art; see, for example, U.S.
Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209,
and 5,084,197.
[0246] In certain embodiments, the dispersants include borated
and/or non-borated succinimides, including those derivatives from
mono-succinimides, bis-succinimides, and/or mixtures of mono- and
bis-succinimides, wherein the hydrocarbyl succinimide is derived
from a hydrocarbylene group such as polyisobutylene having a Mn of
from about 500 to about 5000, or from about 1000 to about 3000, or
about 1000 to about 2000, or a mixture of such hydrocarbylene
groups, often with high terminal vinylic groups. Other dispersants
include succinic acid-esters and amides,
alkylphenol-polyamine-coupled Mannich adducts, their capped
derivatives, and other related components.
[0247] Polymethacrylate or polyacrylate derivatives are another
class of dispersants. These dispersants may be prepared by reacting
a nitrogen containing monomer and a methacrylic or acrylic acid
esters containing about 5 to about 25 carbon atoms in the ester
group. Representative examples are shown in U.S. Pat. Nos.
2,100,993, and 6,323,164. Polymethacrylate and polyacrylate
dispersants may be used as multifunctional viscosity modifiers. The
lower molecular weight versions can be used as lubricant
dispersants or fuel detergents.
[0248] Illustrative dispersants useful in this disclosure include
those derived from polyalkenyl-substituted mono- or dicarboxylic
acid, anhydride or ester, wherein the polyalkenyl moiety has an
average molecular weight of at least about 900 and from greater
than 1.3 to 1.7 (e.g. from greater than 1.3 to 1.6 or from greater
than 1.3 to 1.5) functional groups (mono- or dicarboxylic acid
producing moieties) per polyalkenyl moiety (a medium functionality
dispersant). Functionality (F) can be determined according to the
following formula:
F=(SAP.times.Mn)/((112,200.times.A.I.)-(SAP.times.98)),
wherein: SAP is the saponification number (i.e., the number of
milligrams of KOH consumed in the complete neutralization of the
acid groups in one gram of the succinic-containing reaction
product, as determined according to ASTM D94); Mn is the number
average molecular weight of the starting olefin polymer; and A.I.
is the percent active ingredient of the succinic-containing
reaction product (the remainder being unreacted olefin polymer,
succinic anhydride and diluent).
[0249] The polyalkenyl moiety of the dispersant may have a number
average molecular weight of at least about 900 or suitably at least
about 1500, such as between about 1800 and about 3000 (e.g. between
about 2000 and about 2800, from about 2100 to about 2500, or from
about 2200 to about 2400). The molecular weight of a dispersant is
generally expressed in terms of the molecular weight of the
polyalkenyl moiety. This is because the precise molecular weight
range of the dispersant depends on numerous parameters including
the type of polymer used to derive the dispersant, the number of
functional groups, and the type of nucleophilic group employed.
[0250] Polymer molecular weight, specifically Mn, can be determined
by various known techniques. One convenient method is gel
permeation chromatography (GPC), which additionally provides
molecular weight distribution information (see W. W. Yau, J. J.
Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography", John Wiley and Sons, New York, 1979). Another
useful method for determining molecular weight, particularly for
lower molecular weight polymers, is vapor pressure osmometry (e.g.,
ASTM D3592).
[0251] In an embodiment, the polyalkenyl moiety in a dispersant has
a narrow molecular weight distribution (MWD), also referred to as
polydispersity, as determined by the ratio of weight average
molecular weight (Mw) to number average molecular weight (Mn).
Polymers having a Mw/Mn of less than 2.2 (e.g. less than 2.0) are
most desirable. Suitable polymers have a polydispersity of from
about 1.5 to 2.1 (e.g. from about 1.6 to about 1.8).
[0252] Suitable polyalkenes employed in the formation of the
dispersants include homopolymers, interpolymers or lower molecular
weight hydrocarbons. One family of such polymers comprise polymers
of ethylene and/or at least one C3 to C26 alpha-olefin having the
formula:
H.sub.2C.dbd.CHR.sup.6,
wherein R.sup.6 is a straight or branched chain alkyl radical
comprising 1 to 26 carbon atoms and wherein the polymer contains
carbon-to-carbon unsaturation, and a high degree of terminal
ethenylidene unsaturation. In an embodiment, such polymers comprise
interpolymers of ethylene and at least one alpha-olefin of the
above formula, wherein R.sup.6 is alkyl of from 1 to 18 carbon
atoms (e.g. from 1 to 8 carbon atoms or from 1 to 2 carbon
atoms).
[0253] Another useful class of polymers is polymers prepared by
cationic polymerization of monomers such as isobutene and styrene.
For example, the polymer(s) can be polyisobutenes obtained by
polymerization of a C4 refinery stream having a butene content of
35 to 75% by wt., and an isobutene content of 30 to 60% by wt.
Petroleum feestreams, such as Raffinate II, can be a source of
monomer for making poly-n-butenes. These feedstocks are disclosed
in the art such as in U.S. Pat. No. 4,952,739. Certain embodiments
utilize polyisobutylene prepared from a pure isobutylene stream or
a Raffinate I stream to prepare reactive isobutylene polymers with
terminal vinylidene olefins. Polyisobutene polymers that may be
employed may be based on a polymer chain of from about 1500 to
about 3000.
[0254] In yet further embodiments, the dispersant(s) are
non-polymeric (e.g., mono- or bis-succinimides). Such dispersants
can be prepared by conventional processes, such as those disclosed
in U.S. Patent Application Publication No. 2008/0020950, the
disclosure of which is incorporated herein by reference.
[0255] The dispersant(s) can be borated by conventional means, as
generally disclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and
5,430,105.
[0256] Dispersants may be used in an amount of zero to about 10
weight percent or about 0.01 to about 8 weight percent (e.g. about
0.1 to about 5 weight percent or about 0.5 to about 3 weight
percent). Or such dispersants may be used in an amount of zero to
about 8 weight percent (e.g. about 0.01 to about 5 weight percent
or about 0.1 to about 3 weight percent). On an active ingredient
basis, such additives may be used in an amount of zero to about 10
weight percent (e.g. about 0.3 to about 3 weight percent). The
hydrocarbon portion of the dispersant atoms can range from about
C60 to about C1000, or from about C70 to about C300, or from about
C70 to about C200. These dispersants may contain both neutral and
basic nitrogen, and mixtures thereof. Dispersants can be end-capped
by borates and/or cyclic carbonates. Nitrogen content in the
finished oil can vary from about zero to about 2000 ppm by weight
(e.g. from about 100 ppm by weight to about 1200 ppm by weight).
Basic nitrogen can vary from about zero to about 1000 ppm by weight
(e.g. from about 100 ppm by weight to about 600 ppm by weight).
[0257] Dispersants as described herein are beneficially useful with
the compositions of the present disclosure. Further, in one
embodiment, preparation of the compositions of the present
disclosure using one or more (e.g. 1, 2, 3, 4, or more) dispersants
is achieved by combining ingredients of the present disclosure,
plus optional base stocks and lubricant additives, in a mixture at
a temperature above the melting point of such ingredients,
particularly that of the one or more M-carboxylates (M=H, metal,
two or more metals, mixtures thereof).
[0258] As used herein, the dispersant concentrations are given on
an "as delivered" basis. The active dispersant may be delivered
with a process oil. The "as delivered" dispersant may contain from
about 20 weight percent to about 80 weight percent, or from about
40 weight percent to about 60 weight percent, of active dispersant
in the "as delivered" dispersant product.
[0259] Friction Modifier(s).
[0260] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, or 4, or more) friction modifier. 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. Any friction modifier that is known or that becomes
know may be utilized in the composition of the present
disclosure.
[0261] Friction modifiers may include, for example, organometallic
compounds or materials, or mixtures thereof. Illustrative
organometallic friction modifiers useful in the lubricating turbine
oil formulations of this disclosure include, for example,
molybdenum amine, molybdenum diamine, an organotungstenate, a
molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum
amine complexes, molybdenum carboxylates, and the like, and
mixtures thereof. In an embodiment, tungsten-based compounds are
utilized.
[0262] Other illustrative friction modifiers useful in the
lubricating formulations of the present disclosure include, for
example, alkoxylated fatty acid esters, alkanolamides, polyol fatty
acid esters, borated glycerol fatty acid esters, fatty alcohol
ethers, and mixtures thereof.
[0263] Illustrative alkoxylated fatty acid esters include, for
example, polyoxyethylene stearate, fatty acid polyglycol ester, and
the like. These can include polyoxypropylene stearate,
polyoxybutylene stearate, polyoxyethylene isosterate,
polyoxypropylene isostearate, polyoxyethylene palmitate, and the
like.
[0264] Illustrative alkanolamides include, for example, lauric acid
diethylalkanolamide, palmic acid diethylalkanolamide, and the like.
These can include oleic acid diethyalkanolamide, stearic acid
diethylalkanolamide, oleic acid diethylalkanolamide,
polyethoxylated hydrocarbylamides, polypropoxylated
hydrocarbylamides, and the like.
[0265] Illustrative polyol fatty acid esters include, for example,
glycerol mono-oleate, saturated mono-, di-, and tri-glyceride
esters, glycerol mono-stearate, and the like. These can include
polyol esters, hydroxyl-containing polyol esters, and the like.
[0266] Illustrative borated glycerol fatty acid esters include, for
example, borated glycerol mono-oleate, borated saturated mono-,
di-, and tri-glyceride esters, borated glycerol monosterate, and
the like. In addition to glycerol polyols, these can include
trimethylolpropane, pentaerythritol, sorbitan, and the like. These
esters can be polyol monocarboxylate esters, polyol dicarboxylate
esters, and on occasion polyoltricarboxylate esters. In certain
embodiments, the friction modifier is glycerol mono-oleates,
glycerol dioleates, glycerol trioleates, glycerol monostearates,
glycerol distearates, and glycerol tristearates and the
corresponding glycerol monopalmitates, glycerol dipalmitates,
glycerol tripalmitates, or the respective isostearates, linoleates,
and the like, or combinations thereof. In an embodiment, the
friction modifier is a glycerol esters or mixtures containing any
of these. Ethoxylated, propoxylated, butoxylated fatty acid esters
of polyols, especially using glycerol as underlying polyol can be
utilized.
[0267] Illustrative fatty alcohol ethers include, for example,
stearyl ether, myristyl ether, and the like. Alcohols, including
those that have carbon numbers from C3 to C50, can be ethoxylated,
propoxylated, or butoxylated to form the corresponding fatty alkyl
ethers. The underlying alcohol portion can be, e.g., stearyl,
myristyl, C11-C13 hydrocarbon, oleyl, isosteryl, and the like.
[0268] Other friction modifiers could be optionally included in
addition to the fatty phosphites and fatty imidazolines. A useful
list of such other friction modifier additives is included in U.S.
Pat. No. 4,792,410. U.S. Pat. No. 5,110,488 discloses metal salts
of fatty acids and especially zinc salts, useful as friction
modifiers. Fatty acids are also useful friction modifiers. A list
of other suitable friction modifiers includes at least one of: (i)
fatty phosphonates; (ii) fatty acid amides; (iii) fatty epoxides;
(iv) borated fatty epoxides; (v) fatty amines; (vi) glycerol
esters; (vii) borated glycerol esters; (viii) alkoxylated fatty
amines; (ix) borated alkoxylated fatty amines; (x) metal salts of
fatty acids; (xi) sulfurized olefins; (xii) condensation products
of carboxylic acids or equivalents and polyalkylene-polyamines;
(xiii) metal salts of alkyl salicylates; (xiv) amine salts of
alkylphosphoric acids; (xv) fatty esters; (xvi) condensation
products of carboxylic acids; or equivalents with polyols and
mixtures thereof.
[0269] Representatives of each of these types of friction modifiers
are known and are commercially available. For instance, (i)
includes components of the formulas:
(RO)2PHO,
(RO)(HO)PHO, and
P(OR)(OR)(OR),
wherein, in these structures, the each "R" is conventionally
referred to as an alkyl group, but may also be hydrogen. It is, of
course, possible that the alkyl group is actually alkenyl and thus
the terms "alkyl" and "alkylated," as used herein, will embrace
other than saturated alkyl groups within the component. The
component should have sufficient hydrocarbyl groups to render it
substantially oleophilic. In some embodiments, the hydrocarbyl
groups are substantially un-branched. Many suitable such components
are available commercially and may be synthesized as described in
U.S. Pat. No. 4,752,416. In some embodiments, the component
contains 8 to 24 carbon atoms in each of the R groups. In other
embodiments, the component may be a fatty phosphite containing 12
to 22 carbon atoms in each of the fatty radicals, or 16 to 20
carbon atoms. In one embodiment the fatty phosphite can be formed
from oleyl groups, thus having 18 carbon atoms in each fatty
radical.
[0270] The (iv) borated fatty epoxides are known from Canadian
Patent No. 1,188,704.
[0271] These oil-soluble boron-containing compositions are prepared
by reacting, at a temperature from 80.degree. C. to 250.degree. C.,
boric acid or boron trioxide with at least one fatty epoxide having
the formula:
##STR00009##
wherein each of R.sup.7, R.sup.8, R.sup.9 and R.sup.10 is
independently hydrogen or an aliphatic radical, or any two thereof
together with the epoxy carbon atom or atoms to which they are
attached, form a cyclic radical. In an embodiment, the fatty
epoxide contains at least 8 carbon atoms.
[0272] The borated fatty epoxides can be characterized by the
method for their preparation which involves the reaction of two
materials. Reagent A can be boron trioxide or any of the various
forms of boric acid including metaboric acid (HBO.sub.2),
orthoboric acid (H.sub.3BO.sub.3) and tetraboric acid
(H.sub.2B.sub.40.sub.7). In an embodiment, Reagent A is boric acid,
such as orthoboric acid. Reagent B can be at least one fatty
epoxide having the above formula. In the formula, each of the R
groups is most often hydrogen or an aliphatic radical with at least
one being a hydrocarbyl or aliphatic radical containing at least 6
carbon atoms. The molar ratio of reagent A to reagent B may be
about 1:0.25 to about 1:4 (e.g. about 1:1 to about 1:3 or about
1:2). The borated fatty epoxides can be prepared by merely blending
the two reagents and heating them at temperature of about
80.degree. C. to about 250.degree. C., such as about 100.degree. C.
to about 200.degree. C., for a period of time sufficient for
reaction to take place. If desired, the reaction may be effected in
the presence of a substantially inert, normally liquid organic
diluent. During the reaction, water is evolved and may be removed
by distillation.
[0273] The (iii) non-borated fatty epoxides, corresponding to
Reagent B above, are also useful as friction modifiers.
[0274] Borated amines are generally known from U.S. Pat. No.
4,622,158. Borated amine friction modifiers (including (ix) borated
alkoxylated fatty amines) can be prepared by the reaction of a
boron compounds, as described above, with the corresponding amines.
The amine can be a simple fatty amine or hydroxy containing
tertiary amines. The borated amines can be prepared by adding the
boron reactant, as described above, to an amine reactant and
heating the resulting mixture at about 50.degree. C. to about
300.degree. C. (e.g. about 100.degree. C. to about 250.degree. C.
or about 130.degree. C. to about 180.degree. C.) with stirring. The
reaction is continued until by-product water ceases to evolve from
the reaction mixture indicating completion of the reaction.
[0275] Among the amines useful in preparing the borated amines are
commercial alkoxylated fatty amines known by the trademark
"ETHOMEEN" and available from Akzo Nobel. Representative examples
of these ETHOMEEN.TM. materials is ETHOMEEN.TM. C/12
(bis[2-hydroxyethyl]-coco-amine); ETHOMEEN.TM. C/20
(polyoxyethylene-[10]cocoamine); ETHOMEEN.TM. S/12
(bis[2-hydroxyethyl] soyamine); ETHOMEEN.TM. T/12
(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN.TM. T/15
(polyoxyethylene-[5]tallowamine); ETHOMEEN.TM. 0/12
(bis[2-hydroxyethyl]oleyl-amine); ETHOMEEN.TM. 18/12
(bis[2-hydroxyethyl]-octadecylamine); and ETHOMEEN.TM. 18/25
(polyoxyethylene[15]-octadecylamine). Fatty amines and ethoxylated
fatty amines are also described in U.S. Pat. No. 4,741,848.
Dihydroxyethyl tallowamine (commercially sold as ENT-12.TM.) is
included in these types of amines.
[0276] The (viii) alkoxylated fatty amines, and (v) fatty amines
themselves (such as oleylamine and dihydroxyethyl tallowamine) may
be useful as friction modifiers in this disclosure. Such amines are
commercially available.
[0277] Both borated and unborated fatty acid esters of glycerol can
be used as friction modifiers. The (vii) borated fatty acid esters
of glycerol are prepared by borating a fatty acid ester of glycerol
with boric acid with removal of the water of reaction. In an
embodiment, there is sufficient boron present such that each boron
will react with from 1.5 to 2.5 hydroxyl groups present in the
reaction mixture. The reaction may be carried out at a temperature
in the range of about 60.degree. C. to about 135.degree. C., in the
absence or presence of any suitable organic solvent, such as
methanol, benzene, xylenes, toluene, or oil.
[0278] The (vi) fatty acid esters of glycerol themselves can be
prepared by a variety of methods well known in the art. Many of
these esters, such as glycerol monooleate and glycerol tallowate,
are manufactured on a commercial scale. In a particular embodiment,
the esters are oil-soluble and prepared from C8 to C22 fatty acids
or mixtures thereof, such as are found in natural products and as
are described in greater detail below. In an embodiment, fatty acid
monoesters of glycerol used, although, mixtures of mono- and
diesters may be used. For example, commercial glycerol monooleate
may contain a mixture of 45% to 55% by weight monoester and 55% to
45% diester.
[0279] Fatty acids can be used in preparing the above glycerol
esters; they can also be used in preparing their (x) metal salts,
(ii) amides, and (xii) imidazolines, any of which can also be used
as friction modifiers. In an embodiment, the fatty acids are those
containing 10 to 24 carbon atoms, such as those containing 12 to 18
carbon atoms. The acids can be branched or straight-chain,
saturated or unsaturated. In some embodiments, the acids are
straight-chain acids. In other embodiments, the acids are branched.
Suitable acids include decanoic, oleic, stearic, isostearic,
palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic
acids, and the acids from the natural products tallow, palm oil,
olive oil, peanut oil, corn oil, coconut oil and Neat's foot oil.
In certain embodiments, the acid is oleic acid. In other
embodiments, the metal salts include zinc and calcium salts.
Examples are overbased calcium salts and basic oleic acid-zinc salt
complexes, such as zinc oleate, which can be represented by the
formula Zn.sub.4Oleate.sub.6O.sub.1. In an embodiment, the amides
are those prepared by condensation with ammonia or with primary or
secondary amines such as ethylamine and diethanolamine. Fatty
imidazolines are the cyclic condensation product of an acid with a
diamine or polyamine, such as a polyethylenepolyamine. The
imidazolines may be represented by the structure:
##STR00010##
wherein: R is an alkyl group; and R' is hydrogen or a hydrocarbyl
group or a substituted hydrocarbyl group, including
--(CH.sub.2CH.sub.2NH).sub.n-- groups, wherein n is an integer from
1 to 4. In an embodiment, the friction modifier is the condensation
product of a C10 to C24 fatty acid with a polyalkylene polyamine,
and in particular, the product of isostearic acid with
tetraethylenepentamine.
[0280] The condensation products of carboxylic acids and
polyalkyleneamines (xiii) may be imidazolines or amides. They may
be derived from any of the carboxylic acids described above and any
of the polyamines described herein.
[0281] Sulfurized olefins (xi) are well known commercial materials
used as friction modifiers. A particularly sulfurized olefin
utilized herein is one which is prepared in accordance with the
detailed teachings of U.S. Pat. Nos. 4,957,651 and 4,959,168.
Described therein is a co-sulfurized mixture of 2 or more reactants
selected from the group consisting of (1) at least one fatty acid
ester of a polyhydric alcohol, (2) at least one fatty acid, (3) at
least one olefin, and (4) at least one fatty acid ester of a
monohydric alcohol. Reactant (3), the olefin component, comprises
at least one olefin. This olefin is may be an aliphatic olefin,
which usually will contain 4 to 40 carbon atoms, e.g. from 8 to 36
carbon atoms. For example, terminal olefins, or alpha-olefins,
including those having from 12 to 20 carbon atoms, may be utilized.
Mixtures of these olefins are commercially available, and such
mixtures are contemplated for use in this disclosure. The
co-sulfurized mixture of two or more of the reactants, is prepared
by reacting the mixture of appropriate reactants with a source of
sulfur. The mixture to be sulfurized can contain about 10 to about
90 parts of Reactant (1), or about 0.1 to about 15 parts by weight
of Reactant (2); or about 10 to about 90 parts (e.g. about 15 to
about 60 parts or about 25 to about 35 parts) by weight of Reactant
(3), or about 10 to about 90 parts by weight of reactant (4). The
mixture, in the present disclosure, includes Reactant (3) and at
least one other member of the group of reactants identified as
Reactants (1), (2) and (4). The sulfurization reaction may be
effected at an elevated temperature with agitation and optionally
in an inert atmosphere and in the presence of an inert solvent. The
sulfurizing agents useful in the process of the present disclosure
include elemental sulfur, which maybe hydrogen sulfide, sulfur
halide plus sodium sulfide, and a mixture of hydrogen sulfide and
sulfur or sulfur dioxide. For example, about 0.5 to about 3 moles
of sulfur are employed per mole of olefinic bonds. Sulfurized
olefins may also include sulfurized oils, such as vegetable oil,
lard oil, oleic acid and olefin mixtures.
[0282] Metal salts of alkyl salicylates (xiii) include calcium and
other salts of long chain (e.g. C12 to C16) alkyl-substituted
salicylic acids.
[0283] Amine salts of alkylphosphoric acids (xiv) include salts of
oleyl and other long chain esters of phosphoric acid, with amines
as described below. Useful amines in this regard are
tertiary-aliphatic primary amines, sold under the tradename
Primene.TM..
[0284] In some embodiments, the friction modifier is a fatty acid
or fatty oil, a metal salt of a fatty acid, a fatty amide, a
sulfurized fatty oil or fatty acid, an alkyl phosphate, an alkyl
phosphate amine salt; a condensation product of a carboxylic acid
and a polyamine, a borated fatty epoxide, a fatty imidazoline, or
combinations thereof.
[0285] In other embodiments, the friction modifier may be the
condensation product of isostearic acid and tetraethylene
pentamine, the condensation product of isostearic acid and
1-[tris(hydroxymethyl)]methylamine, borated polytetradecyloxirane,
zinc oleate, hydroxylethyl-2-heptadecenyl imidazoline, dioleyl
hydrogen phosphate, C14-C18 alkyl phosphate or the amine salt
thereof, sulfurized vegetable oil, sulfurized lard oil, sulfurized
oleic acid, sulfurized olefins, oleyl amide, glycerol monooleate,
soybean oil, or mixtures thereof.
[0286] In still other embodiments, the friction modifier may be
glycerol monooleate, oleylamide, the reaction product of isostearic
acid and 2-amino-2-hydroxymethyl-1,3-propanediol, sorbitan
monooleate, 9-octadecenoic acid, isostearyl amide, isostearyl
monooleate or combinations thereof.
[0287] Although their presence is not required to obtain the
benefit of the present disclosure, friction modifiers may be
present in an amount from zero to about 2 wt. % (e.g., about 0.01
wt. % to about 1.5 wt. %) of the composition of the present
disclosure. These ranges may apply to the amounts of individual
friction modifier present in the composition or to the total
friction modifier component in the compositions, which may include
a mixture of two or more friction modifiers.
[0288] Many friction modifiers tend to also act as emulsifiers.
This is often due to the fact that friction modifiers often have
non-polar fatty tails and polar head groups.
[0289] The composition of the present disclosure exhibit desired
properties, e.g., wear control, in the presence or absence of a
friction modifier.
[0290] Although their presence is not required to obtain the
benefit of this disclosure, the friction modifier or friction
modifiers may be present in an amount of about 0.01 weight percent
to about 5 weight percent (e.g. about 0.1 weight percent to about
2.5 weight percent, or about 0.1 weight percent to about 1.5 weight
percent, or about 0.1 weight percent to about 1 weight percent).
Concentrations of molybdenum-containing materials are often
described in terms of Mo metal concentration. Advantageous
concentrations of Mo may range from about 25 ppm to about 700 ppm
or more (e.g. about 50 to about 200 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.
[0291] Molybdenum-Containing Compounds (Friction Reducers).
[0292] Illustrative molybdenum-containing friction reducers useful
in the disclosure include, for example, an oil-soluble decomposable
organo molybdenum compound, such as Molyvan.TM. 855 which is an oil
soluble secondary diarylamine defined as substantially free of
active phosphorus and active sulfur. The Molyvan.TM. 855 is
described in Vanderbilt's Material Data and Safety Sheet as a
organomolybdenum compound having a density of 1.04 and viscosity at
100.degree. C. of 47.12 cSt. The organo molybdenum compounds may be
useful because of their superior solubility and effectiveness.
[0293] Another illustrative molybdenum-containing compound is
Molyvan.TM. L, which is sulfonated oxymolybdenum
dialkyldithiophosphate described in U.S. Pat. No. 5,055,174 hereby
incorporated by reference.
[0294] Molyvan.TM. A made by R. T. Vanderbilt Company, Inc., New
York, N.Y., USA, is also an illustrative molybdenum-containing
compound, which contains about 28.8 wt. % Mo, 31.6 wt. % C, 5.4 wt.
% H., and 25.9 wt. % S. Also useful are Molyvan.TM. 855,
Molyvan.TM. 822, Molyvan.TM. 856, and Molyvan.TM. 807.
[0295] Also useful is Sakura Lube.TM. 500, which is more soluble Mo
dithiocarbamate containing lubricant additive obtained from Asahi
Denki Corporation and comprised of about 20.2 wt. % Mo, 43.8 wt. %
C, 7.4 wt. % H, and 22.4 wt. % S. Sakura Lube.TM. 300, a low sulfur
molybdenum dithiophosphate having a molybdenum to sulfur ratio of
1:1.07, is a molybdenum-containing compound useful in this
disclosure.
[0296] Also useful is Molyvan.TM. 807, a mixture of about 50 wt. %
molybdenum ditridecyldithyocarbonate, and about 50 wt. % of an
aromatic oil having a specific gravity of about 38.4 SUS and
containing about 4.6 wt. % molybdenum, also manufactured by R. T.
Vanderbilt and marketed as an antioxidant and antiwear
additive.
[0297] Other sources are molybdenum Mo(Co).sub.6, and molybdenum
octoate, MoO(C.sub.7H.sub.15CO.sub.2).sub.2 containing about 8 wt-%
Mo marketed by Aldrich Chemical Company, Milwaukee, Wis. and
molybdenum naphthenethioctoate marketed by Shephard Chemical
Company, Cincinnati, Ohio.
[0298] Inorganic molybdenum compounds, such as molybdenum sulfide
and molybdenum oxide, are substantially less preferred than the
organic compounds as described in Molyvan.TM. 855, Molyvan.TM. 822,
Molyvan.TM. 856, and Molyvan.TM. 807.
[0299] Illustrative molybdenum-containing compounds useful in this
disclosure are disclosed, for example, in U.S. Patent Application
Publication No. 2003/0119682, which is incorporated herein by
reference.
[0300] Organo molybdenum-nitrogen complexes may also be included in
the formulations of the present disclosure. 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 an exemplary reaction product of that
disclosure; the spectrum identifies an ester carbonyl band at 1740
cm 1 and an amide carbonyl band at 1620 cm 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.
[0301] 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.
[0302] Although their presence is not required to obtain the
benefit of the present disclosure, molybdenum-containing additives
may be used in an amount of from zero to about 5.0 (e.g.,
.ltoreq.about 5, .ltoreq.about 4, .ltoreq.about 3, .ltoreq.about 2,
or .ltoreq.about 1) percent by mass of the composition of the
present disclosure. For example, the dosage may be up to about
3,000 ppm by mass, such as from about about 100 ppm to about about
2,500 ppm by mass, from about 300 to about 2,000 ppm by mass, or
from about 300 to about 1,500 ppm by mass of molybdenum.
[0303] Borated Ester Compounds.
[0304] In any aspect or embodiment described herein, the
composition of the present disclosure comprises at least one (e.g.,
1, 2, 3, or 4, or more) borated-ester compound. Illustrative
boron-containing compounds useful in the disclosure include, for
example, a borate ester, a boric acid, other boron compounds, such
as a boron oxide. The boron compound is hydrolytically stable and
is utilized for improved antiwear, and performs as a rust and
corrosion inhibitor for copper bearings and other metal engine
components. The borated ester compound acts as an inhibitor for
corrosion of metal to prevent corrosion of either ferrous or
non-ferrous metals (e.g. copper, bronze, brass, titanium, aluminum
and the like) or both, present in concentrations in which they are
effective in inhibiting corrosion.
[0305] Patents describing techniques for making basic salts of
sulfonic, carboxylic acids and mixtures thereof include U.S. Pat.
Nos. 5,354,485; 2,501,731; 2,616,911; 2,777,874; 3,384,585;
3,320,162; 3,488,284; and 3,629,109. The disclosures of these
patents are incorporated herein by reference. Methods of preparing
borated overbased compositions are found in U.S. Pat. Nos.
4,744,920; 4,792,410; and PCT publication WO 88/03144. The
disclosures of these references are incorporated herein by
reference. The oil-soluble neutral or basic salts of alkali or
alkaline earth metals salts may also be reacted with a boron
compound.
[0306] An illustrative borate ester utilized in this disclosure is
manufactured by Exxon-Mobil USA under the product designation of
("MCP 1286") and MOBIL ADC700. Test data show the viscosity at
100.degree. C. using the D-445 method is 2.9 cSt; the viscosity at
40.degree. C. using the D-445 method is 11.9; the flash point using
the D-93 method is 146; the pour point using the D-97 method is
-69; and the percent boron as determined by the ICP method is 5.3%.
The borated ester (Vanlube.TM. 289), which is marketed as an
antiwear/antiscuff additive and friction reducer, is an exemplary
borate ester useful in the disclosure.
[0307] An illustrative borate ester useful in this disclosure is
the reaction product obtained by reacting about 1 mole fatty oil,
about 1.0 to 2.5 moles diethanolamine followed by subsequent
reaction with boric acid to yield about 0.1 to 3 percent boron by
mass. It is believed that the reaction products may include one or
both of the following two primary components, with the further
listed components being possible components when the reaction is
pushed toward full hydration:
##STR00011##
[0308] where R.sub.1.dbd.H or C.sub.xH.sub.y where x=1 to 60, and
y=3 to 121
##STR00012##
wherein Y represents a fatty oil residue. In an embodiment, the
fatty oils are glyceryl esters of higher fatty acids containing at
least 12 carbon atoms (e.g. 22 carbon atoms or more). Such esters
are commonly known as vegetable and animal oils. Vegetable oils
that may be used include oils derived from coconut, corn,
cottonseed, linseed, peanut, soybean and sunflower seed. Similarly,
animal fatty oils such as tallow may be used.
[0309] The source of boron is boric acid or materials that afford
boron and are capable of reacting with the intermediate reaction
product of fatty oil and diethanolamine to form a borate ester
composition.
[0310] While the above organoborate ester composition is
specifically discussed above, it should be understood that other
organoborate ester compositions should also function with similar
effect in the present disclosure, such as those set forth in U.S.
Patent Application Publication No. 2003/0119682, which is
incorporated herein by reference. In addition, dispersions of
borate salts, such as potassium borate, may also be useful.
[0311] Other illustrative organoborate compositions useful in this
disclosure are disclosed, for example, in U.S. Patent Application
Publication No. 2008/0261838, which is incorporated herein by
reference.
[0312] In addition, other illustrative oranoborate compositions
useful in this disclosure are disclosed, for example, U.S. Pat.
Nos. 4,478,732, 4,406,802, 4,568,472 on borated mixed hydroxyl
esters, alkoxylated amides, and amines; U.S. Pat. No. 4,298,486 on
borated hydroxyethyl imidazolines; U.S. Pat. No. 4,328,113 on
borated alkyl amines and alkyl diamines; U.S. Pat. No. 4,370,248 on
borated hydroxyl-containing esters, including GMO; U.S. Pat. No.
4,374,032 on borated hydroxyl-containing hydrocarbyl oxazolines;
U.S. Pat. No. 4,376,712 on borated sorbitan esters; U.S. Pat. No.
4,382,006 on borated ethoxylated amines; U.S. Pat. No. 4,389,322 on
ethoxylated amides and their borates; U.S. Pat. No. 4,472,289 on
hydrocarbyl vicinal diols and alcohols and ester mixtures and their
borates; U.S. Pat. No. 4,522,734 on borates of hydrolyzed
hydrocarbyl epoxides; U.S. Pat. No. 4,537,692 on etherdiamine
borates; U.S. Pat. No. 4,541,941 on mixtures containing vicinal
diols and hydroxyl substituted esters and their borates; U.S. Pat.
No. 4,594,171 on borated mixtures of various hydroxyl and/or
nitrogen containing borates; and U.S. Pat. No. 4,692,257 on various
borated alcohols/diols, all of which are incorporated herein by
reference.
[0313] Although their presence is not required to obtain the
benefit of this disclosure, boron-containing compounds may be
present in an amount of from zero to about 10.0% percent (e.g. from
about 0.01% to about 5% or from about 0.1% to about 3.0%) by weight
of the composition of the present disclosure. An effective
elemental boron range of up to about 1000 ppm or less than about 1%
elemental boron. Thus, in an embodiment, a concentration of
elemental boron is from about 100 to about 1000 ppm (e.g. from
about 100 to about 300 ppm).
[0314] When the grease composition of the present disclosure
includes one or more of the additives discussed herein, the
additive(s) are blended into the composition in an amount
sufficient for it to perform its intended function.
[0315] The weight percent (wt. %) indicated throughout the present
Application is based on the total weight of the composition of the
present disclosure. It is noted that many of the additives are
shipped from the additive manufacturer as a concentrate, containing
one or more additives together, with a certain amount of base oil
diluents. Accordingly, the weight amounts mentioned herein are
directed to the amount of active ingredient (that is the
non-diluent portion of the ingredient).
Example 1 Antioxidant Polymer Preparation
[0316] An antioxidant diphenyl amine monomer mixture containing
N,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine,
N,N-di-(p-tert-octylphenyl)amine,
N-(p-tert-butylphenyl)-N-phenylamine,
N-(p-tert-octylphenyl)-N-phenylamine and
N-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine is charged
together with n-decane to a 3 L glass reactor connected to a
Dean-Stark head with a reflux condenser. The mixture is heated to
135.degree. C. and t-butylperoxide is added dropwise with stirring.
The temperature is maintained at 135.degree. C. to 140.degree. C.
with stirring and t-butanol is distilled off. Samples are removed
and tested for viscosity. Upon reaching a desired viscosity,
unreacted peroxide is removed under reduced pressure, then the
mixture is heated under reduced pressure to remove remaining
volatiles. The diphenyl amine monomer mixture is CAS number
68411-46-1; N-phenyl-benzenamine reaction products with
2,4,4-trimethylpentene.
[0317] The monomer mixture exhibits a viscosity of 9.1 cSt
(monomer). Polymers or oligomers are prepared having viscosities of
21 cSt (inventive sample 1), 81 cSt (inventive sample 2) and 100
cSt (inventive sample 3). Viscosity is kinematic viscosity at
100.degree. C. determined according to ASTM D445.
[0318] The viscosity and Mn of the samples can be controlled by,
e.g., the length of the reaction or the feed of the peroxide.
Example 2
[0319] It is demonstrated that m/z ions in the isolated polymers
and oligomers show a correlation to increased performance in a VIT
test.
[0320] The table below shows that the m/z ion counts at 838, 984
and 911 Daltons are significantly higher than the #4 residue which
has a lower VIT result. The higher the VIT value, the better the
antioxidant
TABLE-US-00002 Sample VIT (h to pvisc 150) 838 894 911 Reference
470 0 0 0 Sample 1 830 296 225 65 Sample 2 797 386 179 65 Sample 3
533 49 65 8
[0321] FIG. 1 shows a trend that VIT performance is better when
there is a greater amount of dimers and trimers as compared to the
amount of higher polymers (4+) in conjunction with the LC/MS data
that yields the 838 and 894 (which corresponds to 837 and 893
Daltons)
Example 3
[0322] A polymeric composition of the present disclosure is
included as a component in a grease formulation as shown below.
TABLE-US-00003 Formulation Details (wt %) Base Stocks 71.5-73%
71.5-73% 71.5-73% Thickener 7-8.5 7-8.5 7-8.5 Additives 13.37 13.37
13.37 (Standard) IRGANOX L57 1.00 2.00 0.00 Inventive 3 0.00 0.00
1.00 Total 100 100 100 Testing Results ASTM D445-Kinematic 220.0
220.0 220.0 Viscosity at 40.degree. C. (cSt) ASTM D217-Penetration,
287.0 287.0 294.0 Worked (0.1 mm) ASTM D5483 PDSC of Greases 23 N/A
17.3 (Isothermal at 210 C.) ASTM D942-Pressure Vessel 1.1 N/A 2.4
Oxidation Test @ 100 hrs (psi drop) ASTM D942-Pressure Vessel 8 N/A
10.4 Oxidation Test @ 100 hrs (psi drop) DIN 51821 FAG FE9 A/1500/
84.0 135.0 6000 @ 140 C. (B50, hours)
[0323] All of the formulations in the above Table are Lithium
complex (thickener type) greases, with ISO Viscosity grades of 220
and an NLGI consistency grade of 2. Common grease thickener types
are simple lithium soap, lithium complex soap, polyurea, calcium
sulfonate, aluminum soap, calcium soap, mixed aluminum/calcium,
clay and polymer thickened. Greases contain, e.g., 70-80%
basestock, 0.1-20% thickener, and 0-20% additives. The data
demonstrates that the inventive example treated at 1% has the same
oxidative performance as the commercial example treated at 1% in
grease bench oxidation tests (ASTM D5483 and D942). However, when
the same greases were tested in the DIN 51821 FAG FE9 test (rig
test--high temperature bearing performance of a grease) the grease
with the inventive example demonstrated superior performance
compare to the grease that contained 1% commercial example and the
grease that contained 2% of the commercial example. This is
unexpected given the equivalent performance in the bench oxidation
testing. According to the above data, the inventive antioxidant
polymercomposition can be utilized in the preparation of a grease
to improve high temperature bearing performance.
* * * * *
References