U.S. patent application number 14/305291 was filed with the patent office on 2014-12-18 for lubricating composition.
The applicant listed for this patent is SHELL OIL COMPANY. Invention is credited to Adam David Mayernick.
Application Number | 20140371117 14/305291 |
Document ID | / |
Family ID | 52019722 |
Filed Date | 2014-12-18 |
United States Patent
Application |
20140371117 |
Kind Code |
A1 |
Mayernick; Adam David |
December 18, 2014 |
LUBRICATING COMPOSITION
Abstract
A lubricating oil composition having improved anti-oxidation
properties comprising: a base oil comprising a Fischer-Tropsch
derived base oil; and an organic dye compound.
Inventors: |
Mayernick; Adam David;
(Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHELL OIL COMPANY |
Houston |
TX |
US |
|
|
Family ID: |
52019722 |
Appl. No.: |
14/305291 |
Filed: |
June 16, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61836331 |
Jun 18, 2013 |
|
|
|
Current U.S.
Class: |
508/110 |
Current CPC
Class: |
C10M 2203/1025 20130101;
C10M 2203/06 20130101; C10M 2205/173 20130101; C10N 2040/12
20130101; C10N 2030/18 20130101; C10N 2030/10 20130101; C10M 107/02
20130101; C10M 171/007 20130101; C10N 2040/08 20130101; C10N
2040/30 20130101; C10M 2203/10 20130101; C10N 2040/04 20130101;
C10M 169/04 20130101; C10M 2205/0285 20130101; C10M 2203/1025
20130101; C10N 2020/02 20130101; C10M 2203/1025 20130101; C10N
2020/02 20130101 |
Class at
Publication: |
508/110 |
International
Class: |
C10M 107/02 20060101
C10M107/02 |
Claims
1. A lubricating oil composition comprising: (a) a base oil
comprising a Fischer-Tropsch derived base oil; and (b) an organic
dye compound.
2. The lubricating oil composition according to claim 1, wherein
the organic dye compound comprises an organic dye dissolved in a
hydrocarbon solvent or petroleum distillate.
3. The lubricating oil composition according to claim 1, wherein
the the organic dye compound is present in an amount of between
about 0.0001 and 0.001% by weight of the lubricant composition.
4. The lubricating oil composition according to claim 2, wherein
the organic dye is dissolved in kerosene.
5. The lubricating oil composition according to claim 2, wherein
the hydrocarbon solvent is selected from xylene, dimethylbenzene,
and ethylbenzene.
6. The lubricating oil composition according to claim 1, wherein
the organic dye compound is a low flash dye.
7. The lubricating oil composition according to claim 1, wherein
the organic dye compound is a high flash dye.
8. A lubricating oil composition according to any of claims 1 to 8
wherein the Fischer-Tropsch derived base oil has a kinematic
viscosity at 100.degree. C. of from 1 mm.sup.2/s to 35
mm.sup.2/s.
9. A lubricating oil composition according to any of claims 1 to 8
wherein the base oil contains more than 50 wt. %, preferably more
than 60 wt. %, more preferably more than 70 wt. %, even more
preferably more than 80 wt. %, most preferably more than 90 wt. %
Fischer-Tropsch derived base oil.
10. Use of a lubricating oil composition according to any of claims
1 to 8 for providing improved anti-oxidation properties, as
determined by ASTM D6186-08.
11. Use of a lubricating oil composition according to any of claims
1 to 8 for providing improved deposit reduction properties, as
determined according to ASTM D7097-09 or JPI-5S-55-99.
12. Use of a lubricating oil composition according to any of claims
1 to 8 for providing improved foaming performance.
13. Use of a lubricating oil composition according to any of claims
1 to 8 for providing improved air release.
14. A method for lubricating a, the method comprising the step of
lubricating said engine with the oil composition of any of claims
1-8, wherein the step of lubricating the engine results in a
reduction of the amount of oxidation products that are formed.
15. A method for lubricating an engine, the method comprising the
step of lubricating said engine with the oil composition of any of
claims 1-8, wherein the step of lubricating the engine results in a
reduction in the amount of deposits that are formed.
16. A method for lubricating an engine, the method comprising the
step of lubricating said engine with the oil composition of any of
claims 1-8, wherein the step of lubricating the engine results in
improved foaming performance.
17. A method for lubricating an engine, the method comprising the
step of lubricating said engine with the oil composition of any of
claims 1-8, wherein the step of lubricating the engine results in
improved air release.
Description
[0001] This non-provisional application claims priority from U.S.
Provisional Application Ser. No. 61/836331 filed Jun. 18, 2013
which is hereby incorporated by reference in its entirety.
[0002] The present invention relates to a lubricating composition,
in particular a lubricating composition having improved oxidation
stability, foaming performance, air release, demulsibility,
filterability, corrosion reduction, and deposit reduction.
[0003] As is disclosed in for example D. J. Wedlock et al.,
"Gas-to-Liquids Base Oils to assist in meeting OEM requirements
2010 and beyond", presented at the 2nd Asia-Pacific base oil
Conference, Beijing, China, 23-25 Oct. 2007, the use of
Fischer-Tropsch derived base oils in lubricating compositions such
as engine oils, transmission fluids, and industrial lubricants can
result in various performance benefits. Examples of performance
benefits by the use of Fischer-Tropsch derived base oils mentioned
in the above article include: improved oxidation properties,
improved engine cleanliness, improved wear protection, improved
emissions and improved after-treatment device compatibility. Also
the Fischer-Tropsch base oils allow for the formulation of
low-viscosity energy conserving formulations.
[0004] Fischer-Tropsch derived base oils are highly paraffinic API
group III base oils (API Base Oil Interchangeability Guidelines)
exhibiting very good cold flow properties, high oxidative
stability, and high viscosity indices. However, due to the high
paraffin content the solvency of the base oils is generally low,
resulting in incompatibility with other lubricant components and
additives.
[0005] Fischer-Tropsch base oils may have relatively low solvency.
As used herein the term "solvency" in relation to a base oil means
the ability of that base oil to dissolve various performance
additives or, for that matter, dissolve any component that may
potentially "desolvate" and form solids or a second liquid phase,
including oxidation byproducts. Thus, in one embodiment, it would
be desirable to develop lubricating compositions having increased
solvency at the same time as exhibiting the other performance
benefits mentioned above, in particular improved oxidation
stability and reduced piston deposits.
[0006] One or more of the above or other objects can be obtained by
a lubricating oil composition comprising: [0007] (a) a base oil
selected from Group III base oils, Group IV polyalphaolefins, or a
combination thereof; and [0008] (b) between 0.0001 and 0.001 wt %
of an organic dye compound.
[0009] In certain embodiments, the lubricating oil composition can
include a solvent in which the organic dye compounds can be
dissolved. In certain embodiments, the lubricating oil composition
can further include an antioxidant, wherein the antioxidant can be
selected from aminic antioxidants, phenolic antioxidants, and
mixtures thereof. In certain embodiments, the lubricant composition
can further include one or more detergent compounds having a TBN
(total base number equivalent, as determined by ASTM D2896) in the
range of from 0-400.
[0010] It has surprisingly been found that the lubricating
compositions according to the present invention exhibit improved
oxidation stability, foaming performance, air release,
demulsibility, filterability, corrosion reduction, and deposit
reduction.
[0011] The lubricant composition described herein can find a
variety of uses as a lubricant, including but not limited to,
lubrication of transmissions, turbines, air compressors, hydraulic
systems, and the like.
[0012] The base oil used in the lubricating composition according
to the present invention is selected from a Group III base oil, a
polyalphaolefin, and mixtures thereof. The base oil used in the
present invention may conveniently comprise mixtures of one or more
Group III base oils and/or polyalphaolefins, thus, according to the
present invention, the term "base oil" may refer to a mixture
containing more than one base oil. Suitable base oils for use in
the lubricating oil composition of the present invention are Group
III mineral base oils, Group IV poly-alpha olefins (PAOs), Group
III Fischer-Tropsch derived base oils, and mixtures thereof.
[0013] By "Group III" and "Group IV" base oils in the present
invention are meant lubricating oil base oils according to the
definitions of American Petroleum Institute (API) for category III
and IV. These API categories are defined in API Publication 1509,
15th Edition, Appendix E, April 2002.
[0014] Fischer-Tropsch derived base oils are known in the art. By
the term "Fischer-Tropsch derived" is meant that a base oil is, or
is derived from, a synthesis product of a Fischer-Tropsch process.
A Fischer-Tropsch derived base oil may also be referred to as a GTL
(Gas-To-Liquids) base oil. Suitable Fischer-Tropsch derived base
oils that may be conveniently used as the base oil in the
lubricating composition of the present invention include those, for
example, disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO
00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO
00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO
01/57166.
[0015] Typically, the aromatics content of a Fischer-Tropsch
derived base oil, suitably determined by ASTM D 4629, will be less
than about 1 wt. %, alternatively less than about 0.5 wt. % or in
alternate embodiments, less than about 0.1 wt. %. Suitably, the
base oil has a total paraffin content of at least about 80 wt. %,
alternatively at least about 85 wt. %, alternatively at least about
90 wt. %, alternatively at least about 95 wt. %, or, in certain
embodiments, at least about 99 wt. %. The Fischer-Tropsch derived
base oil suitably has a saturates content (as measured by IP-368,
ASTM D2007, ASTM D7419, or any other chromatographic method that
will yield similar results) of greater than about 98 wt. %,
alternatively greater than about 99 wt. %, or alternatively greater
than about 99.5 wt. %. The Fischer-Tropsch derived base oil can
further include a maximum n-paraffin content of about 0.5 wt. % and
naphthenic compound content of from 0 to less than 20 wt. %,
alternatively from about 0.5 to 10 wt. %, alternatively from about
1-5 wt. %, or alternatively from about 5-10 wt. %.
[0016] Typically, the Fischer-Tropsch derived base oil or base oil
blend has a kinematic viscosity at 100.degree. C. (as measured by
ASTM D 7042) in the range of from 1 to 35 mm.sup.2/s (cSt),
alternatively from 1 to 25 mm.sup.2/s (cSt), alternatively from 2
to 20 mm.sup.2/s (cSt), or alternativley from 2 mm.sup.2/s to 12
mm.sup.2/s. The Fischer-Tropsch derived base oil can have a
kinematic viscosity at 100.degree. C. (as measured by ASTM D 7042)
of at least 2.5 mm.sup.2/s, alternativley at least 3.0 mm.sup.2/s
(e.g., "GTL 3". In certain embodiments of the present invention,
the Fischer-Tropsch derived base oil can have a kinematic viscosity
at 100.degree. C. of not greater than 5.0 mm.sup.2/s, alternatively
not greater than 4.5 mm.sup.2/s, alternatively not greater than 4.2
mm.sup.2/s (e.g., "GTL 4"). In certain embodiments of the present
invention, the Fischer-Tropsch derived base oil has a kinematic
viscosity at 100.degree. C. of not greater than 8.5 mm.sup.2/s,
alternatively not greater than 8 mm.sup.2/s (e.g., "GTL 8"). Other
grades of GTL products would also be possible, based upon the
specific distillation process utilized to produce the GTL
product.
[0017] Further, the Fischer-Tropsch derived base oil can have a
kinematic viscosity at 40.degree. C. (as measured by ASTM D 7042)
of from 10 to 100 mm.sup.2/s (cSt), alternatively from 15 to 50
mm.sup.2/s, alternatively from 50 to 80 mm.sup.2/s, alternatively
greater than 100 mm.sup.2/s.
[0018] Also, in certain embodiments, the Fischer-Tropsch derived
base oil can have a pour point (as measured according to ASTM D
5950) of less than about -10.degree. C., alternatively less than
about -20.degree. C., alternatively less than about -30.degree. C.,
alternativley less than about -40.degree. C., and alternatively
less than about -45.degree. C.
[0019] The flash point (as measured by ASTM D92) of the
Fischer-Tropsch derived base oil can be greater than 120.degree.
C., alternatively greater than 140.degree. C.
[0020] The Fischer-Tropsch derived base oil can have a viscosity
index (according to ASTM D 2270) in the range of from about 100 to
200. Alternativley, the Fischer-Tropsch derived base oil can have a
viscosity index of at least 125, alternatively at least 130. In
certain embodiments, the viscosity index is less than 180,
alternatively less than 160, alternatively less than 150.
[0021] In the event the Fischer-Tropsch derived base oil contains a
blend of two or more Fischer-Tropsch derived base oils, the above
values apply to the blend of the two or more Fischer-Tropsch
derived base oils.
[0022] Poly-alpha olefin base oils (PAOs) and their manufacture are
well known in the art. In certain embodiments, the poly-alpha
olefin base oils used in the lubricating compositions of the
present invention may be derived from linear C.sub.2 to C.sub.32,
preferably C.sub.6 to C.sub.16, alpha olefins. Alternatively,
feedstocks for said poly-alpha olefins can be 1-octene, 1-decene,
1-dodecene and 1-tetradecene.
[0023] In certain embodiments, the base oil as used in the
lubricating composition can include a first GTL base oil, and may
optionally include one or more of the oils selected from PAO, or
Group I, II, III or V base oils.
[0024] In certain embodiments, it may be preferable to use a
Fischer-Tropsch derived base oil instead of a PAO base oil, in view
of the high cost to manufacture PAOs. Thus, preferably, the base
oil contains more than 50 wt. %, preferably more than 60 wt. %,
more preferably more than 70 wt. %, even more preferably more than
80 wt. %, and most preferably more than 90 wt. % of a
Fischer-Tropsch derived base oil. In an alternate embodiment, not
more than 5 wt. %, alternatively not more than 2 wt. %, of the base
oil is not a Fischer-Tropsch derived base oil. In certain preferred
embodiments, 100 wt % of the base oil is based on one or more
Fischer-Tropsch derived base oils.
[0025] Preferably the base oil or base oil blend that includes the
Fischer-Tropsch derived base oil has a kinematic viscosity at
100.degree. C. of between 2 and 35 cSt, alternatively between 2 and
10.5 cSt (according to ASTM D 445).
[0026] In addition to the Group III base oil and/or polyalphaolefin
base oil, the lubricating composition may include one or more other
types of mineral derived or synthetic base oils, including Group I,
II, IV and V base oils according to the definitions of American
Petroleum Institute (API). These API categories are defined in API
Publication 1509, 15th Edition, Appendix E, July 2009.
[0027] In certain embodiments, the total amount of base oil that is
incorporated in the lubricating composition of the present
invention is preferably an amount in the range of from 60 to 99 wt.
%, alternatively an amount in the range of from 65 to 90 wt. %, and
in certain preferred embodiments, in an amount in the range of from
70 to 85 wt. %, with respect to the total weight of the lubricating
composition.
[0028] The lubricating oil composition also includes an oil soluble
organic dye. The organic dye can include functional groups that
serves as chromophores that absorb and transmit wavelengths in the
visible spectrum. Exemplary dyes that can be used in the
lubricating oil composition of the present invention can generally
be placed in two catagories based upon the solvent volatility: low
flash dyes and high flash dyes. Exemplary low flash dyes can
include those sold under the tradename "Unisol", such as Unisol
Blue A (United Color Manufacturing, Inc.), and dyes sold under the
tradename "Automate", such as Automate Red GXS (Dow Chemical
Company). Exemplary high flash dyes can includes those sold under
the tradename "Unisol", such as Unisol Blue AHF (United Color
Manufacturing, Inc.) and dyes sold under the tradename "Novalube",
such as Novalube Yellow 326.
[0029] In certain embodiments the organic dyes can be first
dissolved in an organic solvent prior to being added to the base
oil. Exemplary organic solvents can include hydrocarbon solvents
having relatively low flash points, such as xylene,
dimethylbenzene, ethylbenzene, and the like. Exemplary low flash
solvents typically have a flash point of less than about
200.degree. F. Exemplary high flash solvents typically have a flash
point of greater than about 200.degree. F. Other exemplary organic
solvents can include petroleum distillates, such as kerosene. In
certain embodiments, the amount of solvent that can be added to the
organic dye can be between 10 and 90% by weight, alternatively
between about 10 and 30% by weight, alternatively between about 30
and 60% by weight, alternatively between about 60 and 90% by
weight.
[0030] The organic dyes can be present in an amount of between
about 0.0001 wt. % and 0.001 wt. % as measured relative to the
total weight of the lubricant composition, alternatively between
about 0.0001 wt. % and 0.0005 wt. %, alternatively between about
0.0005 wt. % and 0.001 wt. %. In certain embodiments, two or more
organic dyes can be present in the lubricant composition, wherein
the total concentration of the organic dyes is between about 0.0001
wt. % and 0.001 wt. %, as measured relative to the total weight of
the lubricant composition, alternatively between about 0.0001 wt. %
and 0.0005 wt. %, alternatively between about 0.0005 wt. % and
0.001 wt. %.
[0031] Optionally, the lubricating oil compositions of the present
invention can also include a solvency booster. As used herein, the
term "solvency booster" means a component which enhances the
solvency of the Group III/PAO base oil with respect to certain
additives that are included in the formulation. The use of a
solvency booster in the lubricating composition of the present
invention can be particularly useful when the base oil is selected
from a Fischer-Tropsch derived base oil.
[0032] In certain embodiments, the solvency booster is present in
an amount of 30 wt % or less, preferably 20 wt % of less, more
preferably 15 wt % or less, by weight of the lubricating oil
composition. The solvency booster is preferably present at a level
of 1 wt % or more, more preferably 3 wt % or more, even more
preferably 5 wt % or more, by weight of the lubricating oil
composition. Alternatively, the solvency booster is present in an
amount of between about 1 and 30 wt %, alternatively in an amount
of between about 2 and 20 wt %, or alternatively in an amount
between about 5 and 15 wt %.
[0033] Compounds suitable for use as a solvency booster can be
selected from alkylated aromatic compounds, naphthenic base oils,
ester base oils, and mixtures thereof.
[0034] Preferred alkylated aromatic compounds for use as a solvency
booster herein can include alkylated benzenes, alkylated
anthracenes, alkylated phenanthrenes, alkylated biphenyls, and
alkylated naphthalenes and mixtures thereof.
[0035] Alkylated naphthalenes may be produced by any suitable means
known in the art, from naphthalene itself or from substituted
naphthalenes which may contain one or more short chain alkyl groups
having up to about eight carbon atoms, for example methyl, ethyl,
and propyl. Suitable alkyl-substituted naphthalenes include
alphamethylnaphthalene, dimethylnaphthalene, and ethylnaphthalene.
Naphthalene itself is especially suitable since the resulting
mono-alkylated products have better thermal and oxidative stability
than the more highly alkylated materials. Suitable alkylated
naphthalene lubricant compositions are described in U.S. Pat. No.
3,812,036, and U.S. Pat. No. 5,602,086. The preparation of
alkylnaphthalenes is further disclosed in U.S. Pat. No.
4,714,794.
[0036] The alkylated aromatic compound for use herein can be
selected from alkylbenzene compounds, alkylnaphthalene compounds,
and mixtures thereof.
[0037] The alkylaromatic component preferably has a kinematic
viscosity at 100.degree. C. in the range of from 3 to 12
mm.sup.2/s, more preferably in the range of from 3.8 to 7
mm.sup.2/s. The viscosity index of the alkylaromatic component is
above 40, preferably at or above 70.
[0038] An exemplary alkylated aromatic compound for use herein is
an alkylnaphthalene compound. Examples of commercially available
alkylnaphthalene compounds are those under the tradename NA-Lube
(King Industries), such as NA-Lube KR 008, NA-Lube KR019, and the
like, and those under the tradename Mobil MCP (ExxonMobil).
[0039] Examples of commercially available alkyl benzenes include
those available under the tradename Fusyn-22 (Formosan), those
available under the tradename Janex HAL (Janex), and those
available under the tradename ZEROL (Shreive Chemical Products,
Inc. (SCP)).
[0040] Suitable naphthenic base oils for use as a solvency booster
herein includes naphthenic base oils having low viscosity index
(VI), typically between about 40-80, and a low pour point, for
example, a temperature of less than -20.degree. C. Such base oils
can be produced from feedstocks rich in naphthenes and low in wax
content. There is no particular limitation on the type of
mineral-derived naphthenic base oil which can be used in the base
oil composition herein. Any mineral-derived naphthenic base oil
which is suitable for use in a lubricating oil composition can be
used herein. Naphthenic base oils are defined as Group V base oils
according to API. Such mineral-derived base oils can be obtained by
refinery processes starting from naphthenic crude feeds.
Mineral-derived naphthenic base oils for use herein preferably have
a pour point of below -20.degree. C. and a viscosity index of less
than 70. Such base oils can be produced from feedstocks rich in
naphthenes and low in wax content. Mineral-derived naphthenic base
oils are well known and described in more detail in "Lubricant base
oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc,
New York, 1994, ISBN 0-8247-9256-4, pages 28-35. Methods of
manufacture of naphthenic base oils can be found in "Lubricants and
Lubrication (Second, Completely Revised and Extended Edition)",
published by Wiley-VCH Verlag GmbH & Co. KgaA, Chapter 4, pages
46-48.
[0041] An example of a suitable naphthenic base oil for use as a
solvency booster herein is that commercially available under the
tradename KN4006 (China National Petroleum Corporation). Other
examples of suitable naphthenic base oils for use as a solvency
booster herein include those available under the tradenames
Hydrocal, Hydrosol and HR Tufflo (Calumet Specialty Products), and
those commercially available under the tradename Nynas (Nynas Oil
Company).
[0042] Suitable esters for use as a solvency booster herein include
natural and synthetic esters such as diesters and polyol esters. An
example of a suitable ester for use as a solvency booster herein is
the saturated polyol ester commercially available under the
tradename Priolube 3970 (Croda International PLC). Other suitable
esters for use as a solvency booster herein include those available
under the tradename Radialube (Oleon), those available under the
tradename Emery (from Emery) and those available under the
tradename Esterex (ExxonMobil Chemical).
[0043] The lubricating oil compositions of the present invention
can include one or more detergent compounds having a TBN (total
base number equivalent, as determined by ASTM D2896) of between
about 0 and 400. In certain embodiments, the detergent compound can
include one or more alkaline earth metal salicylate.
[0044] Suitable alkaline earth metal salicylates include calcium,
magnesium and barium salicylates, and mixtures thereof, preferably
calcium salicylates.
[0045] The lubricating oil compositions of the present invention
preferably include from 0.01 wt % to 9 wt %, more preferably from 1
wt % to 6 wt %, even more preferably from 3.5 wt % to 5.5 wt %, of
a detergent, by weight of the lubricating oil composition.
[0046] The level of an alkaline earth metal salicylate having a TBN
in the range of from 150 to 250 is preferably in the range of 0.01
wt % to 5 wt %, more preferably from 1 wt % to 3 wt %, by weight of
the lubricating oil composition.
[0047] In certain embodiments, the detergent can be an alkaline
earth metal salicylate having a TBNE (total base number equivalent,
as determined by ASTM D2896) in the range of from 250 to 400, and
is preferably in the range of 0.01 wt % to 3 wt %, more preferably
from 1 wt % to 2 wt %, by weight of the lubricating oil
composition.
[0048] In certain embodiments, the lubricating oil compositions of
the present invention can include one or more anti-oxidants.
Suitable anti-oxidants for use herein include phenolic antioxidants
and/or aminic antioxidants.
[0049] In one embodiment, said antioxidants are present in an
amount in the range of from 0.1 to 5.0 wt. %, preferably in an
amount in the range of from 0.3 to 3.0 wt. %, and more preferably
in an amount of in the range of from 0.5 to 1.5 wt. %, based on the
total weight of the lubricating oil composition.
[0050] Examples of aminic antioxidants which may be conveniently
used include alkylated diphenylamines,
phenyl-.alpha.-naphthylamines, phenyl-.beta.-naphthylamines and
alkylated .alpha.-naphthylamines
[0051] Exemplary aminic antioxidants include dialkyldiphenylamines,
such as p,p'-dioctyl-diphenylamine,
p,p'-di-.alpha.-methylbenzyl-diphenylamine, and
N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines,
such as mono-t-butyldiphenylamine and mono-octyldiphenylamine,
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, 1-naphthylamine,
arylnaphthylamines, such as 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 and 3,7-dioctylphenothiazine.
[0052] Preferred aminic antioxidants include those available under
the following trade designations: "Sonoflex OD-3" (Seiko Kagaku
Co.), "Irganox L-57" (Ciba Specialty Chemicals Co.) and
phenothiazine (Hodogaya Kagaku Co.).
[0053] Exemplary phenolic antioxidants that may be used include
C7-C9 branched alkyl esters of
3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid,
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,
2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol,
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-hydroxybenzylmercaptooctylacetate,
alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionates such as
n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
n-butyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and
2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,6-d-t-butyl-.alpha.-dimethylamino-p-cresol,
2,2'-methylenebis(4-alkyl-6-t-butylphenol) such as
2,2'-methylenebis(4-methyl-6-t-butylphenol, and
2,2-methylenebis(4-ethyl-6-t-butylphenol), bisphenols such as
4,4'-butylidenebis(3-methyl-6-t-butylphenol,
4,4'-methylenebis(2,6-di-t-butylphenol),
4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane,
2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,
4,4'-cyclohexylidenebis(2,6-t-butylphenol),
hexamethyleneglycol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
triethyleneglycolbis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate],
2,2'-thio-[[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionylox-
ylethyl}2,4,8,10-tetraoxaspiro[5,5]undecane,
4,4'-thiobis(3-methyl-6-t-butylphenol) and
2,2'-thiobis(4,6-di-t-butylresorcinol), polyphenols such as
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)-butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
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''-hydr-
oxyphenyl)methyl-6-t-butylphenol and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, and
p-t-butylphenol-formaldehyde condensates and
p-t-butylphenol-acetaldehyde condensates.
[0054] Phenolic antioxidants include those available under the
following trade designations: "Irganox L-135" (Ciba Specialty
Chemicals Co.), "Yoshinox SS" (Yoshitomi Seiyaku Co.), "Antage
W-400" (Kawaguchi Kagaku Co.), "Antage W-500" (Kawaguchi Kagaku
Co.), "Antage W-300" (Kawaguchi Kagaku Co.), "Irganox L-109" (Ciba
Speciality Chemicals Co.), "Tominox 917" (Yoshitomi Seiyaku Co.),
"Irganox L-115" (Ciba Speciality Chemicals Co.), "Sumilizer GA80"
(Sumitomo Kagaku), "Antage RC" (Kawaguchi Kagaku Co.), "Irganox
L-101" (Ciba Speciality Chemicals Co.), "Yoshinox 930" (Yoshitomi
Seiyaku Co.).
[0055] The lubricating oil composition of the present invention may
include mixtures of one or more phenolic antioxidants with one or
more aminic antioxidants.
[0056] According to the present invention, the lubricating
composition preferably includes up to about 30 wt % of a viscosity
modifier, based on the total weight of the lubricating composition.
In one embodiment, the lubricating composition comprises from 20 wt
% to 30 wt % of a viscosity modifier. In another embodiment, the
lubricating composition includes up to about 20 wt % of a viscosity
modifier. In an alternate embodiment, the lubricating composition
includes between about 10 and 20 wt % of a viscosity modifier. In
yet another emobidment, the lubricating composition includes
between about 1 and 10 wt % of a viscosity modifier. In a preferred
embodiment of the present invention, the lubricating composition is
essentially free of viscosity modifier. In a particularly preferred
embodiment of the present invention, the lubricating composition
comprises 0 wt % of a viscosity modifier.
[0057] Examples of viscosity index improvers include copolymers of
alpha-olefins and dicarboxylic acid esters such as those described
in U.S. Pat. No. 4,931,197. Commercially available copolymers of
alpha-olefins and dicarboxylic acid diesters include the Ketjenlube
polymer esters available from Italmatch (and previously Akzo Nobel
Chemicals). Other suitable examples of viscosity index improvers
are polyisobutylenes; commercially available polyisobutylenes
include the Oloa.RTM. products (Chevron Oronite).
[0058] Further examples of viscosity index improvers which may
conveniently be used in the lubricating compositions of the present
invention include the styrene-butadiene stellate copolymers,
styrene-isoprene stellate copolymers and the polymethacrylate
copolymers and ethylene-propylene copolymers (also known as olefin
copolymers) of the crystalline and non-crystalline type.
[0059] Suitable olefin copolymers include those commercially
available under the trade designation "PARATONE.RTM." (such as
"PARATONE.RTM. 8921" and "PARATONE.RTM. 8941") (Chevron Oronite
Company LLC); those commercially available under the trade
designation "HiTEC.RTM." (such as "HiTEC.RTM. 5850B") (Afton
Chemical Corporation); and those commercially available under the
trade designation "Lubrizol.RTM. 7067C" (The Lubrizol Corporation).
Suitable polyisoprene polymers include those commercially available
under the trade designation "SV200" (Infineum International Ltd.).
Suitable diene-styrene copolymers include those commercially
available under the trade designation "SV 260" (Infineum
International Ltd).
[0060] The compositions herein may also include one or more
anti-wear additives. Suitable anti-wear additives for use herein
include zinc dithiophosphate compounds selected from zinc dialkyl-,
diaryl- and/or alkylaryl-dithiophosphates, molybdenum-containing
compounds, and ashless anti-wear additives such as substituted or
unsubstituted thiophosphoric acids, and salts thereof.
[0061] Examples of ashless thiophosphates are known in the art.
These compounds are metal-free organic compounds. Suitable ashless
thiophosphates for use in the lubricating oil composition of the
present invention may include esters and/or salts of thiophosphoric
acids, and substituted thiophosphoric acids. Preferably, the
ashless thiophosphates are substituted by one or more hydrocarbyl
groups which hydrocarbyl groups can optionally contain an acid, a
hydroxy and/or an ester group. The hydrocarbyl moiety preferably is
an alkyl group containing up to 12 carbon atoms. The
hydrocarbyl-substituted thiophosphate preferably contains 2 or 3
hydrocarbyl groups, or is a mixture of thiophosphates containing 2
and 3 hydrocarbyl groups.
[0062] The ashless thiophosphates can contain any number of sulphur
atoms directly linked to the phosphorus atom. Preferably, the
thiophosphates are monothiophosphates and/or dithiophosphates.
[0063] Examples of ashless thiophosphates which may be conveniently
used in the lubricating oil composition of the present invention
are described in EP-A-0375324, U.S. Pat. Nos. 5,922,657, 4,333,841
and 5,093,016, and may be conveniently made according to the
methods described therein.
[0064] Examples of commercially available ashless thiophosphates
that may be conveniently used in the lubricating oil composition of
the present invention include those available under the trade
designations "IRGALUBE L-63" and "IRGALUBE 353" (Ciba Specialty
Chemicals) and that available under the trade designation "LZ 5125"
(Lubrizol).
[0065] In certain embodiments, the lubricating composition can
include one or more anti-wear additives selected from one or more
zinc dithiophosphates. The or each zinc dithiophosphate may be
selected from zinc dialkyl-, diaryl- or
alkylaryl-dithiophosphates.
[0066] Examples of zinc dithiophosphates which are commercially
available include those available under the trade designations "Lz
677A", "Lz 1095", "Lz 1097", "Lz 1370", "Lz 1371", "Lz 1373" and
"Lz 1395" (Lubrizol Corp.), those available under the trade
designations "OLOA 260", "OLOA 262", "OLOA 267" and "OLOA 269R"
(Chevron Oronite), and those available under the trade designation
"HITEC 7169" and "HITEC 7197" (Afton Chemical).
[0067] Preferably, the lubricating composition according to the
present invention includes a phosphorus containing compound,
preferably selected from the group consisting of phosphonates,
phosphates, phosphites, phosphorothionates and dithiophosphates,
and combinations thereof. Examples of commercially available
dithiophosphates and phosphates are "IRGALUBE 63" and IRGALUBE
349", respectively, both available from Ciba Specialty
Chemicals.
[0068] The lubricating oil composition of the present invention has
a kinematic viscosity at 40.degree. C. in the range of from 2
mm.sup.2/s to 220 mm2/s, preferably in the range of from 32
mm.sup.2/s to 220 mm.sup.2/s.
[0069] In addition to the components mentioned above, the
lubricating composition according to the present invention may
further include one or more additional additives such as
anti-oxidants, dispersants, detergents, extreme-pressure additives,
friction modifiers, viscosity index improvers, pour point
depressants, metal passivators, corrosion inhibitors, demulsifiers,
anti-foam agents, seal compatibility agents and additive diluent
base oils, etc.
[0070] As the person skilled in the art is familiar with the above
and other additives, these are not further discussed here in
detail.
[0071] Specific examples of such additives are described in for
example Kirk-Othmer Encyclopedia of Chemical Technology, third
edition, volume 14, pages 477-526.
[0072] The above-mentioned additives are typically present in an
amount in the range of from 0.01 to 35.0 wt. %, based on the total
weight of the lubricating composition, preferably in an amount in
the range of from 0.05 to 25.0 wt. %, more preferably from 0.1 to
20.0 wt. %, based on the total weight of the lubricating
composition.
[0073] The lubricating compositions of the present invention may be
conveniently prepared by admixing the one or more additives with
the base oil(s).
[0074] The lubricating composition according to the present
invention may be used in various applications, such as a
transmission oil, a grease, a hydraulic oil, an industrial gear
oil, a turbine oil, a compressor oil, and the like.
[0075] In another aspect, the present invention provides a method
for improving one or more of oxidation stability and deposit
reduction properties, which method includes lubricating with a
lubricating composition according to one aspect of the invention.
In another aspect, the present invention provides the use of a
lubricating composition as described herein, for improving one or
more of oxidation stability properties (for example, as determined
by ASTM D6186-98) and deposit reduction properties (for example, as
determined according to ASTM D7097-09 or JPI-5S-55-99).
[0076] In another aspect, the present invention provides a method
for improving foam performance, generally defined as a lower
propensity of the lubricant composition to form foam, and a less
stable foam upon formation (as determined by ASTM D892). Similarly,
in another aspect, the present invention provides a method for
improving air release, generally defined as a lower propensity of
the lubricant composition to retain air, and generally retaining
air for a shorter amount of time. In another aspect, the present
invention provides a method for improving demulsibility, generally
defined as the lowering the propensity of the lubricant composition
to form stable emulsions. The demulsibility is typically measured
by the ability of a mixture of the lubricant composition and water
to form two separate layers. In alternate embodiments, the present
invention provides a method for improving the filterability of the
lubricant composition, wherein the improved filterability is
demonstrated by a lower potential of the lubricant composition to
block or plug filtration media.
[0077] The present invention is described below with reference to
the following Examples, which are not intended to limit the scope
of the present invention in any way.
EXAMPLES
Lubricating Oil Compositions
[0078] Various combinations of additives, base oils and solvency
boosters were formulated. Table 1 shows the properties of the base
oils.
[0079] "Base oil 1" (or "BO1" or "GTL 4") was a Fischer-Tropsch
derived base oil having a kinematic viscosity at 100.degree. C.
(ASTM D445) of approximately 3.89 cSt (mm.sup.2s.sup.-1). Base oil
1 may be conveniently manufactured by the process described in e.g.
WO-A-02/070631, the teaching of which is hereby incorporated by
reference.
[0080] "Base oil 2" (or "BO2") was a commercially available Group
III base oil having a kinematic viscosity at 100.degree. C. (ASTM
D445) of approximately 4.3 cSt. Base oil 2 is commercially
available from e.g. SK Energy (Ulsan, South Korea) under the trade
designation Yubase 4.
[0081] "Base oil 3" or (GTL 3) was a Fischer-Tropsch derived base
oil having having a kinematic viscosity at 100.degree. C. (ASTM
D445) of approximately 2.700 cSt (mm.sup.2s.sup.-1). Base oil 3 may
be conveniently manufactured by the process described in e.g.
WO-A-02/070631, the teaching of which is hereby incorporated by
reference.
[0082] "Base oil 4" or (GTL 8) was a Fischer-Tropsch derived base
oil having having a kinematic viscosity at 100.degree. C. (ASTM
D445) of approximately 4.000 cSt (mm.sup.2s.sup.-1). Base oil 4 may
be conveniently manufactured by the process described in e.g.
WO-A-02/070631, the teaching of which is hereby incorporated by
reference.
TABLE-US-00001 TABLE 1 Base Base oil 2 Base oil 1 (Yubase oil 3
Base oil 4 (GTL 4) 4) (GTL 3) (GTL 8) Kinematic viscosity at 16.91
19.49 9.930 43.51 40.degree. C..sup.1 [cSt] Kinematic viscosity at
3.89 4.3 2.707 7.613 100.degree. C..sup.1 [cSt] VI Index.sup.2 127
126 112 144 Pour point.sup.3 [.degree. C.] -39 -18 -39 -21 Noack
volatility.sup.4 [wt. %] 11.2 14.2 46.8 2.1 Saturates.sup.5 [wt. %]
99.2 99.3 99.9 99.9 Tertiary Carbon, %.sup.6 18.1 n.d. n.d. n.d.
Secondary Carbon, %.sup.6 66.7 n.d. n.d. n.d. Primary Carbon,
%.sup.6 14.3 n.d. n.d. n.d. Epsilon carbon content, %.sup.6 12.1
n.d. n.d. n.d. n- and iso-paraffins.sup.7 92.35 n.d. n.d. n.d.
Mono-naphthenics.sup.7 6.85 n.d. n.d. n.d. di- and
poly-naphthenics.sup.7 0.87 n.d. n.d. n.d. Aromatics.sup.5 0.5 n.d.
n.d. n.d. Dynamic viscosity at -20.degree. C..sup.8 n.d. 713 n.d.
n.d. [cP] Dynamic viscosity at -25.degree. C..sup.8 n.d. 931 n.d.
n.d. [cP] Dynamic viscosity at -30.degree. C..sup.8 948 n.d. n.d.
5010 [cP] Dynamic viscosity at -35.degree. C..sup.8 1580 n.d. n.d.
9340 [cP] .sup.1According to ASTM D 445 .sup.2According to ASTM D
2270 .sup.3According to ASTM D 5950 .sup.4According to CEC
L-40-A-93/ASTM D 5800 .sup.5According to IP 368 (modified)
.sup.6According to 13C NMR .sup.7According to FIMS .sup.8According
to ASTM D 5293 n.d. = not determined
HPDSC-OIT Test
[0083] In order to measure the oxidation stability properties of
the various lubricating compositions set out in Table 2, the
lubricating compositions were subjected to the HPDSC-OIT (High
Pressure Differential Scanning calorimetry) test according to ASTM
D6186-08, at a temperature of 200.degree. C., and oxygen at 200
psig).
[0084] Improved anti-oxidation properties are evidenced by greater
oxidation induction time (OIT).
Foaming Performance
[0085] In order to measure the foaming performance, the lubricating
compositions were subjected to a foaming test according to ASTM
D892.
Air Release
[0086] In order to measure the air release performance, the
lubricating compositions were subjected to an air release test
according to ASTM D3427.
Results
[0087] Samples were prepared that included mineral (Yubase 4) and
synthetic (GTL4) base oils and between 0.0001 and 0.001 wt. % of
the dyes.
[0088] Results show the lubricant compositions of the present
invention which include GTL4 and Unisol high flash organic dye show
improved oxidative stability, as measured according to ASTM
D6186-08, relative to similar lubricant compositions that include
mineral base oils. Furthermore, the GTL4 base oil lubricants having
Unisol high flash organic dye unexpectedly show a non-linear
relationship with respect to the oxidative stability and the amount
of dye present in the lubricant formulation. Samples having Unisol
high flash organic dye compounds present require reduced amounts of
anti-oxidants than do either lubricant compositions that either do
not include organic dye compounds or lubricant compositions that
include organic dye compounds and a mineral base oil.
[0089] The lubricant compositions of the present invention also
show improved foaming performance, relative to similar compositions
having a mineral base oil. Compositions that include both a GTL
base oil and Unisol high flash organic dye compound unexpectedly
show reduced foaming, and less stable foam volume values, as
compared with similar mineral base oils. In certain embodiments,
lubricant compositions having a concentration of Unisol high flash
organic dye of 0.0005 wt. % showed a reduction in the amount of
foam produced.
[0090] Lubricant compositions of the present invention also show
improved air release, as demonstrated by a shorter air release
time, relative to those lubricant compositions that do not include
organic dye compounds or a GTL base oil. For example, compounds of
the present invention having both a GTL base oil and Unisol high
flash organic dye compound at a concentration of 0.0005 wt. %
exhibit air release times that are lower than similar compositions
that do not include organic dye compounds.
* * * * *