U.S. patent application number 14/589032 was filed with the patent office on 2015-07-09 for lubricating composition.
The applicant listed for this patent is SHELL OIL COMPANY. Invention is credited to Adam David MAYERNICK.
Application Number | 20150191671 14/589032 |
Document ID | / |
Family ID | 53494686 |
Filed Date | 2015-07-09 |
United States Patent
Application |
20150191671 |
Kind Code |
A1 |
MAYERNICK; Adam David |
July 9, 2015 |
LUBRICATING COMPOSITION
Abstract
A lubricating oil composition that includes a base oil
comprising a Fischer-Tropsch derived base oil and an anti-corrosive
compound. The anti-corrosive compound can be present in an amount
between 0.001 and 8% by weight, preferably between 1 and 5% by
weight.
Inventors: |
MAYERNICK; Adam David;
(Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHELL OIL COMPANY |
Houston |
TX |
US |
|
|
Family ID: |
53494686 |
Appl. No.: |
14/589032 |
Filed: |
January 5, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61924501 |
Jan 7, 2014 |
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Current U.S.
Class: |
508/279 ;
508/514; 508/517 |
Current CPC
Class: |
C10M 2215/04 20130101;
C10M 2215/223 20130101; C10N 2030/12 20130101; C10M 2219/106
20130101; C10M 2223/04 20130101; C10M 2223/045 20130101; C10M
133/44 20130101; C10M 169/04 20130101; C10N 2010/04 20130101; C10M
2207/123 20130101; C10M 2205/173 20130101; C10M 2215/06 20130101;
C10M 2207/125 20130101; C10N 2010/02 20130101; C10M 2219/068
20130101; C10M 2207/16 20130101; C10M 2215/224 20130101; C10M
2227/061 20130101; C10M 2215/042 20130101; C10M 2219/044 20130101;
C10M 2219/10 20130101; C10N 2040/25 20130101; C10M 2209/103
20130101; C10N 2020/02 20130101 |
International
Class: |
C10M 133/44 20060101
C10M133/44 |
Claims
1. A lubricating oil composition comprising: (a) a base oil
comprising a Fischer-Tropsch derived base oil; and (b) an
anti-corrosive compound.
2. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is present in an amount of between 0.01
and 8% by weight of the lubricant composition.
3. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is selected from the group consisting
of thiazoles, triazoles, benzodiazoles, benzotriazoles, and
thiodiazoles.
4. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is selected from the group consisting
of sodium sulfonates, barium sulfonate, neutral barium
dinonylnaphthalene sulfonate (also calcium and zinc), and overbased
sulfonates.
5. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is selected from the group consisting
of zinc diamyldithiocarbamate and zinc dithiocarbamates.
6. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is selected from the group consisting
of hexamine, phenylenediamine, dimethylethanolamine, and
derivatives thereof.
7. The lubricating oil composition according to claim 1, wherein
the anti-corrosive compound is selected from the group consisting
of phosphate esters, borate esters and polyethers.
8. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from the group consisting of
ethoxylated phenols, substituted succinic acids, fatty carboxylic
acids, carboxylic acid derivatives, and fatty amines such as alkyl
imidazoline.
9. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from the group consisting of
thiophosphates, phosphoric acid derivatives, and zinc
dithiophosphates.
10. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from the group consisting of
zinc naphthenate and bismuth naphthenate.
11. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from mercapto-thiadiazole
derivatives.
12. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is a sarcosine.
13. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from the group consisting of
salts of carboxylic acid and alkanolamine, amine phosphate, and
fatty acid alkanolamines.
14. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is selected from the group consisting of
triethanolamine salts of phosphate esters.
15. The lubricating composition according to claim 1, wherein the
anti-corrosive compound is an oil soluble complex chelating
agent.
16. A lubricating oil composition according to claim 1 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.
17. A lubricating oil composition according to claim 1 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.
18. A method for lubricating an engine, the method comprising
lubricating said engine with the oil composition of claim 1,
wherein the step of lubricating the engine results in a reduction
in the amount of copper corrosion.
19. The method of claim 18, wherein the engine is a passenger car
engine.
20. The method of claim 18, wherein the engine is a heavy duty
diesel engine.
Description
[0001] The present invention relates to a lubricating composition,
in particular a lubricating composition having improved oxidation
stability, demulsibility, filterability, corrosion reduction, and
deposit reduction.
[0002] 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.
[0003] 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,
often resulting in incompatibility with other lubricant components
and additives.
[0004] 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.
[0005] One or more of the above or other objects can be obtained by
a lubricating oil composition comprising:
(a) a base oil selected from Group III base oils, Group IV
polyalphaolefins, or a combination thereof; and (b) between 0.0001
and 10 wt % of a corrosion inhibiting compound.
[0006] In certain embodiments, the lubricating oil composition can
include a solvent in which the corrosion inhibiting compound 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.
[0007] 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, engine oil rust
reduction, copper corrosion reduction and deposit reduction.
[0008] The lubricant composition described herein can find a
variety of uses as a lubricant, including but not limited to,
passenger car engine oils, heavy duty diesel engine oils,
transmission lubricants, turbine oils, air compressor lubricants,
hydraulic fluids, gear oils, greases, transformer oils, marine
lubricants, and the like.
[0009] 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.
[0010] 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.
[0011] 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.
[0012] Typically, the aromatics content of a Fischer-Tropsch
derived base oil, as 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. %. The base oil can
have 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 can have 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. %.
[0013] 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 alternatively 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, alternatively 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.
[0014] 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.
[0015] 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.,
alternatively less than about -40.degree. C., and alternatively
less than about -45.degree. C.
[0016] 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 130.degree. C., alternatively
greater than 140.degree. C.
[0017] 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. In
certain embodiments, the viscosity index can be between 125 and
180, alternatively between 130 and 160.
[0018] 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.
[0019] 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.
[0020] 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.
[0021] 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.
[0022] 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).
[0023] 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.
[0024] 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.
[0025] 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. In certain embodiments the organic dyes can be
first dissolved in an organic solvent prior to being added to the
base oil. 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.
[0026] 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. In certain embodiments,
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 %.
Compounds suitable for use as a solvency booster can be selected
from alkylated aromatic compounds, naphthenic base oils, ester base
oils, and mixtures thereof.
[0027] 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.
[0028] The alkylated aromatic compound for use herein can be
selected from alkylbenzene compounds, alkylnaphthalene compounds,
and mixtures thereof.
[0029] 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.
[0030] 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).
[0031] 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)).
[0032] 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.
[0033] 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).
[0034] 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).
[0035] 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. Suitable
alkaline earth metal salicylates include calcium, magnesium and
barium salicylates, and mixtures thereof, preferably calcium
salicylates.
[0036] In certain embodiments of the present invention, the
lubricant composition can include from 0.001 to 8% by weight of a
corrosion inhibitor. In certain embodiments, exemplary corrosion
inhibitors include, but are not limited to, thiazoles, triazoles,
benzodiazoles, benzotriazoles, and thiodiazoles. In alternate
embodiments, exemplary corrosion inhibitors can include, but are
not limited to, sodium sulfonates barium sulfonate, neutral barium
dinonylnaphthalene sulfonate (also calcium and zinc), and overbased
sulfonates. In other embodiments, exemplary corrosion inhibitors
can include, but are not limited to, ethoxylated phenols,
substituted succinic acids, fatty carboxylic acids, carboxylic acid
derivatives, and fatty amines such as alkyl imidazoline. In yet
other embodiments, exemplary corrosion inhibitors can include, but
are not limited to, phosphate esters, borate esters, and
polyethers. In other embodiments, exemplary corrosion inhibitors
can include, but are not limited to, zinc diamyldithiocarbamate and
zinc dithiocarbamates. In other embodiments, exemplary corrosion
inhibitors can include, but are not limited to, thiophosphates,
phosphoric acid derivatives, and zinc dithiophosphates. In yet
other embodiments, exemplary corrosion inhibitors can include, but
are not limited to, zinc naphthenate and bismuth naphthenate. In
other embodiments, exemplary corrosion inhibitors can include, but
are not limited to, mercapto-thiadiazole derivatives. In other
embodiments, exemplary corrosion inhibitors can include, but are
not limited to, sarcosines. Alternatively, in certain embodiments,
exemplary corrosion inhibitors can include, but are not limited to,
salts of carboxylic acid and alkanolamine, amine phosphate, and
fatty acid alkanolamines. In other embodiments, exemplary corrosion
inhibitors can include, but are not limited to, hexamine,
phenylenediamine, dimethylethanolamine, and derivatives thereof.
Alternatively, exemplary corrosion inhibitors can include, but are
not limited to, triethanolamine salt of phosphate esters. In other
embodiments, an exemplary corrosion inhibitors include, but are not
limited to, oil soluble complex chelating agents, such as
N-salicylidene-propylenediamine.
[0037] Exemplary commercial corrosion inhibitors for use in the
lubricant compositions of the present invention include, but are
not limited to, Irgamet 30 (BASF), Bismuth naphthenate B (PCAS),
Lubad 1365 (Mirachema Nuodex), Valirex Bi 17% naphthenate
(Unicore), Dailube Z500 (Zn 5.2%, DIC), Soligen Zinc 11-12% S
(OMG), Sarkosyl O (BASF), Irgamet 39 (BASF), Irgacor NPA (BASF),
and Irgacor L12 (BASF).
[0038] 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.
[0039] 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.
[0040] 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.
[0041] 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.
[0042] 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.
[0043] Examples of aminic antioxidants which may be conveniently
used include alkylated diphenylamines,
phenyl-.quadrature.-naphthylamines, phenyl-.beta.-naphthylamines
and alkylated .quadrature.-naphthylamines.
[0044] 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.
[0045] 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.).
[0046] 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'-methylene-bis(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-methyl-phenyl)propionylo-
xy]ethyl}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.
[0047] 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.).
[0048] The lubricating oil composition of the present invention may
include mixtures of one or more phenolic antioxidants with one or
more aminic antioxidants.
[0049] 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 embodiment, 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.
[0050] 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).
[0051] 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.
[0052] 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).
[0053] 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.
[0054] 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.
[0055] The ashless thiophosphates can contain any number of sulphur
atoms directly linked to the phosphorus atom. Preferably, the
thiophosphates are monothiophosphates and/or dithiophosphates.
[0056] 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.
[0057] 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).
[0058] 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.
[0059] 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).
[0060] In certain embodiments, 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.
[0061] 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.
[0062] 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.
[0063] As the person skilled in the art is familiar with the above
and other additives, these are not further discussed here in
detail.
[0064] Specific examples of such additives are described in for
example Kirk-Othmer Encyclopedia of Chemical Technology, third
edition, volume 14, pages 477-526.
[0065] 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.
[0066] The lubricating compositions of the present invention may be
conveniently prepared by admixing the one or more additives with
the base oil(s).
[0067] 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.
[0068] 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).
[0069] 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.
[0070] In one embodiment is provided a lubricating oil composition
that includes: (a) a base oil that includes a Fischer-Tropsch
derived base oil; and (b) an anti-corrosive compound. In certain
embodiments, the anti-corrosive compound is present in an amount of
between 0.001 and 8%, preferably between 0.01 and 8% by weight of
the lubricant composition, alternatively in an amount of between 1
and 8% by weight of the lubricant composition, alternatively in an
amount of between 1 and 3% by weight of the lubricant composition,
alternatively in an amount of between 1 and 5% by weight of the
lubricant composition, alternatively in an amount of between 3 and
5% by weight of the lubricant composition, or alternatively in an
amount of between 5 and 8% by weight of the lubricant
composition.
[0071] In another embodiment, is provided a lubricating oil
composition that includes (a) a base oil that includes a
Fischer-Tropsch derived base oil; and (b) an anti-corrosive
compound. In certain embodiments, the anti-corrosive compound is
selected from the group consisting of thiazoles, triazoles,
benzodiazoles, benzotriazoles, and thiodiazoles; alternatively the
anti-corrosive compound is selected from the group consisting of
sodium sulfonates, barium sulfonate, neutral barium
dinonylnaphthalene sulfonate (also calcium and zinc), and overbased
sulfonates; alternatively the anti-corrosive compound is selected
from the group consisting of zinc diamyldithiocarbamate and zinc
dithiocarbamates; alternatively the anti-corrosive compound is
selected from the group consisting of hexamine, phenylenediamine,
dimethylethanolamine, and derivatives thereof; alternatively the
anti-corrosive compound is selected from the group consisting of
phosphate esters, borate esters and polyethers; alternatively the
anti-corrosive compound is selected from the group consisting of
ethoxylated phenols, substituted succinic acids, fatty carboxylic
acids, carboxylic acid derivatives, and fatty amines such as alkyl
imidazoline; alternatively the anti-corrosive compound is selected
from the group consisting of thiophosphates, phosphoric acid
derivatives, and zinc dithiophosphates; alternatively the
anti-corrosive compound is selected from the group consisting of
zinc naphthenate and bismuth naphthenate; alternatively the
anti-corrosive compound is selected from mercapto-thiadiazole
derivatives; alternatively the anti-corrosive compound is a
sarcosine; alternatively the anti-corrosive compound is selected
from the group consisting of salts of carboxylic acid and
alkanolamine, amine phosphate, and fatty acid alkanolamines;
alternatively the anti-corrosive compound is selected from the
group consisting of triethanolamine salts of phosphate esters; or
alternatively the anti-corrosive compound is an oil soluble complex
chelating agent.
[0072] In certain embodiments of the lubricant oil compositions of
the present invention, 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. In certain other embodiments of the lubricant oil
compositions of the present invention, 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. In
yet other embodiments, the lubricant oils of the present invention
provide improved anti-oxidation properties, as determined by ASTM
D6186-08; alternatively providing improved rust prevention, as
determined by ASTM D6557, or alternatively providing improved
copper corrosion prevention, as determined by ASTM D130.
[0073] Also provided is a method for lubricating an engine, the
method comprising the step of lubricating said engine with the oil
compositions described, wherein the step of lubricating the engine
results in a reduction of the amount of oxidation products that are
formed, alternatively wherein the step of lubricating the engine
results in a reduction in the amount of deposits that are formed;
alternatively wherein the step of lubricating the engine results in
a reduction in the amount of engine rust that is formed;
alternatively wherein the step of lubricating the engine results in
a reduction in the amount of copper corrosion; or alternatively
wherein the step of lubricating the engine results in a reduction
in the amount of copper corrosion. In certain instances, the
lubricant oil compositions of the present invention can be utilized
in a passenger car engine, alternatively in a heavy duty diesel
engine, alternatively in a transmission, alternatively in a
turbine, alternatively in an air compressor, alternatively as a
hydraulic fluid, alternatively as a gear oil, alternatively as a
grease, alternatively in a transformer, or alternatively in marine
applications.
EXAMPLES
Lubricating Oil Compositions
[0074] Various combinations of additives, base oils and solvency
boosters were formulated. Table 1 shows the properties of the base
oils.
[0075] "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.
[0076] "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.
[0077] "Base oil 3" or (GTL 3) was a Fischer-Tropsch derived base
oil 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.
[0078] "Base oil 4" or (GTL 8) was a Fischer-Tropsch derived base
oil 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 oil 1 Base oil 2 Base oil 3 Base oil 4
(GTL 4) (Yubase 4) (GTL 3) (GTL 8) Kinematic viscosity 16.91 19.49
9.930 43.51 at 40.degree. C..sup.1 [cSt] Kinematic viscosity 3.89
4.3 2.707 7.613 at 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 11.2 14.2 46.8 2.1 [wt. %] 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 12.1 n.d. n.d. n.d.
content, %.sup.6 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- 0.87 n.d.
n.d. n.d. naphthenics.sup.7 Aromatics.sup.5 0.5 n.d. n.d. n.d.
Dynamic viscosity n.d. 713 n.d. n.d. at -20.degree. C..sup.8 [cP]
Dynamic viscosity n.d. 931 n.d. n.d. at -25.degree. C..sup.8 [cP]
Dynamic viscosity 948 n.d. n.d. 5010 at -30.degree. C..sup.8 [cP]
Dynamic viscosity 1580 n.d. n.d. 9340 at -35.degree. C..sup.8 [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
Copper Corrosion Test
[0079] In order to measure the copper corrosion prevention
performance of the various lubricating compositions set out herein,
the lubricating compositions were subjected to the ASTM D130 test
at a temperature of 250.degree. C. and a period of 1 hour. In this
test method, a polished copper strip is immersed in a specific
volume of the sample being tested and heated under conditions of
temperature and time that are specific to the class of material
being tested. At the end of the heating period, the copper strip is
removed, washed and the colour and tarnish level assessed against
the ASTM Copper Strip Corrosion Standard.
[0080] Improved copper corrosion prevention is evidenced by a lower
copper corrosion designation number.
Examples 1-3 and Comparative Examples 1-3
[0081] Table 2 below shows the formulations of Examples 1-3 and
Comparative Examples 1-3 and the results when these formulations
were subjected to the copper corrosion test ATSM D130. In Table 2,
Irgamet 30, Irgacor NPA and Sarkosyl O are all corrosion
inhibitors. Irgamet 30 and Irgacor NPA are commercially available
from BASF and Sarkosyl O is available from CIBA.
TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Example
1 Example 2 Example 3 Example 1 Example 2 Example 3 Component: (wt
%) (wt %) (wt %) (wt %) (wt %) (wt %) Base Oil 1 (GTL 4) 99.9 99.99
99.95 Base Oil 2 (Yubase 4) 99.95 99.99 99.9 Irgamet 30 0.1 0.1
Sarkosyl O 0.01 0.01 Irgacor NPA 0.05 0.05 Total 100 100 100 100
100 100 ASTM D130 1A 1A 1A 1A 1B 1A (1 hour at 150.degree. C.)
DISCUSSION
[0082] In the copper corrosion test ASTM D130, 1A is the lowest
copper corrosion designation number in this test (the lower the
copper corrosion designation number the lower the corrosion). From
Table 2 it can be seen that Comparative Example 2 gives a worse
result (1B) (i.e. more corrosion) than the other examples.
* * * * *