U.S. patent application number 14/268663 was filed with the patent office on 2014-11-20 for diester-based engine oil formulations with improved low noack and cold flow properties.
This patent application is currently assigned to Chevron U.S.A. Inc.. The applicant listed for this patent is Saleh Ali Elomari, Stephen Joseph Miller, John Michael Rosenbaum, Yalin Yao, Zhen Zhou. Invention is credited to Saleh Ali Elomari, Stephen Joseph Miller, John Michael Rosenbaum, Yalin Yao, Zhen Zhou.
Application Number | 20140342961 14/268663 |
Document ID | / |
Family ID | 51896244 |
Filed Date | 2014-11-20 |
United States Patent
Application |
20140342961 |
Kind Code |
A1 |
Miller; Stephen Joseph ; et
al. |
November 20, 2014 |
DIESTER-BASED ENGINE OIL FORMULATIONS WITH IMPROVED LOW NOACK AND
COLD FLOW PROPERTIES
Abstract
The present invention is generally directed to diester-based
multi-grade engine oil formulations. The diesters employed have a
number a performance benefits in lubricant applications--among
them: biodegradability, extreme temperature performance, oxidative
stability, solubility for additives and deposit and sludge
precursors, flash and fire points. However, ester usage in
lubricants has been quite limited due to their high cost. We
utilize new proprietary diesters, structurally different from
traditional diesters, which are made from fatty acids and alpha
olefins in simple processing steps, yet feature performance similar
to more traditional lubricant esters.
Inventors: |
Miller; Stephen Joseph; (San
Francisco, CA) ; Elomari; Saleh Ali; (Fairfiled,
CA) ; Yao; Yalin; (Danville, CA) ; Rosenbaum;
John Michael; (Richmond, CA) ; Zhou; Zhen;
(Fairfield, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Miller; Stephen Joseph
Elomari; Saleh Ali
Yao; Yalin
Rosenbaum; John Michael
Zhou; Zhen |
San Francisco
Fairfiled
Danville
Richmond
Fairfield |
CA
CA
CA
CA
CA |
US
US
US
US
US |
|
|
Assignee: |
Chevron U.S.A. Inc.
San Ramon
CA
|
Family ID: |
51896244 |
Appl. No.: |
14/268663 |
Filed: |
May 2, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61824004 |
May 16, 2013 |
|
|
|
Current U.S.
Class: |
508/496 |
Current CPC
Class: |
C10N 2030/02 20130101;
C10N 2030/74 20200501; C10M 2207/283 20130101; C10M 2203/1025
20130101; C10M 111/02 20130101; C10N 2030/08 20130101; C10N 2040/25
20130101; C10M 2203/1006 20130101; C10N 2030/10 20130101; C10M
2203/1025 20130101; C10N 2020/02 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101 |
Class at
Publication: |
508/496 |
International
Class: |
C10M 105/36 20060101
C10M105/36 |
Claims
1. A multi-grade engine oil comprising: a) a diester component,
comprising a quantity of at least one diester species having the
following structure: ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3
and R.sub.4 are the same or independently selected from C.sub.2 to
C.sub.17 hydrocarbon groups; b) a second base oil; and c) an
additive package, wherein the second base and third base oil are
independently selected from the group consisting of Group I base
oil, Group II base oil or Group III base oil.
2. The multi-grade engine oil of claim 1, wherein a quantity of at
least one diester species comprises a mixture of isomers where
R.sub.1 and R.sub.2 are different for each isomer.
3. The multi-grade engine oil of claim 1, further comprising, a
third base oil.
4. The multi-grade engine oil of claim 1, wherein the diester has a
Noack Volatility between about 6 and 10 wt %, a CCS Viscosity at
-30.degree. C. between about 700 and 2000 cP, a pour point less
than about -10.degree. C., a cloud point less than about
-10.degree. C., a kinematic viscosity at 100.degree. C. between
about 2.5 to 6.5 centistokes, a VI greater than about 110 and a BN
Oxidator greater than about 20 hours.
5. The multi-grade engine oil according to claim 1 or 3, wherein
the second base and third base oil are independently selected from
the group consisting of light neutral base oil, medium neutral base
oil, Yubase 4, Yubase 6, 150R, 600R, 110RLV, 220R and 100R.
6. The multi-grade engine oil of claim 1, meeting the
specifications for SAE viscosity grade 0W-XX or 5W-XX, wherein XX
represents the integer 16, 20, 30, or 40.
7. The multi-grade engine oil of claim 1, wherein the multi-grade
engine oil meets the SAE J300 standards as revised in January
2009.
8. The multi-grade engine oil of claim 1, having: a) a viscosity
index between about 140-200; b) a kinematic viscosity at
100.degree. C. between about 6-10 cSt; c) a Pour Point less than
about -30.degree. C.; and d) a Noack volatility of less than about
15 wt %, wherein the multi-grade engine oil is a 0W-SAE grade with
a CCS Viscosity at -35.degree. C. less than about 6200 cP or the
multi-grade engine oil is a 5W-SAE grade with a CCS Viscosity at
-30.degree. C. less than about 6600 cP.
9. The multi-grade engine oil of claim 1, wherein the kinematic
viscosity of the multi-grade engine oil at a temperature of
100.degree. C. is between about 3 to 10 centistokes.
10. The multi-grade engine oil of claim 1, wherein the CCS
Viscosity at -30.degree. C. less than about 6,600 cP.
11. The multi-grade engine oil of claim 1, wherein the CCS
Viscosity at -35.degree. C. less than about 6,200 cP.
12. The multi-grade engine oil of claim 1, wherein the Noack
Volatility less than about 15 wt %.
13. The multi-grade engine oil of claim 1, wherein R.sub.1 and
R.sub.2 are selected to have a combined carbon number of from 6 to
16 and R.sub.3 and R.sub.4 are selected to have a combined carbon
number of from 10 to 34.
14. The multi-grade engine oil of claim 1, wherein R.sub.1 and
R.sub.2 of Formula I are selected to have a combined carbon number
of C.sub.16, C.sub.14 or C.sub.12 and R.sub.3 and R.sub.4 are
independently selected from the group consisting of C.sub.12 and a
mixture of C.sub.6-C.sub.10.
15. The multi-grade engine oil of claim 1, wherein the at least one
diester species is derived from a C.sub.8 to C.sub.18 olefin and a
C.sub.6 to C.sub.14 carboxylic acid.
16. The multi-grade engine oil of claim 2, wherein said composition
comprises quantities of at least two different diester isomers.
17. The multi-grade engine oil of claim 1, wherein the at least one
diester species has a molecular mass that is from at least about
340 a.m.u. to at most about 780 a.m.u.
18. The multi-grade engine oil of claim 1, wherein the at least one
diester species is selected from the group consisting of decanoic
acid 2-decanoyloxy-1-hexyl-octyl ester and its isomers,
tetradecanoic acid-1-hexyl-2-tetradecanoyloxy-octyl esters and its
isomers, dodecanoic acid 2-dodecanoyloxy-1-hexyl-octyl ester and
its isomers, hexanoic acid 2-hexanoyloxy-1-hexy-octyl ester and its
isomers, octanoic acid 2-octanoyloxy-1-hexyl-octyl ester and its
isomers, hexanoic acid 2-hexanoyloxy-1-pentyl-heptyl ester and
isomers, octanoic acid 2-octanoyloxy-1-pentyl-heptyl ester and
isomers, decanoic acid 2-decanoyloxy-1-pentyl-heptyl ester and
isomers, decanoic acid-2-cecanoyloxy-1-pentyl-heptyl ester and its
isomers, dodecanoic acid-2-dodecanoyloxy-1-pentyl-heptyl ester and
isomers, tetradecanoic acid 1-penty-2-tetradecanoyloxy-heptyl ester
and isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxy-hexy
ester and isomers, dodecanoic acid-1-butyl-2-dodecanoyloxy-hexyl
ester and isomers, decanoic acid 1-butyl-2-decanoyloxy-hexyl ester
and isomers, octanoic acid 1-butyl-2-octanoyloxy-hexyl ester and
isomers, hexanoic acid 1-butyl-2-hexanoyloxy-hexyl ester and
isomers, tetradecanoic acid 1-propyl-2-tetradecanoyloxy-pentyl
ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl
ester and isomers, decanoic acid 2-decanoyloxy-1-propyl-pentyl
ester and isomers, octanoic acid 1-2-octanoyloxy-1-propyl-pentyl
ester and isomers, hexanoic acid 2-hexanoyloxy-1-propyl-pentyl
ester and isomers, and mixtures thereof.
19. The multi-grade engine oil of claim 1, wherein the multi-grade
engine oil is formulated as a 0W-20 SAE 0W-16 or 5W-20 SAE engine
oil.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a multi-grade engine oils
formulated to meet the specifications for SAE viscosity grade 0W-XX
or 5W-XX engine oil, wherein XX represents the integer 16, 20, 30,
or 40. Formulations meeting the specifications for SAE viscosity
grade 0W-20 and 5W-20 have been successfully prepared using the
present invention. This desired properties achieved include
multi-grade 0W-20 and 5W-20 SAE motor oils with low Noack and
excellent cold flow properties.
BACKGROUND OF THE INVENTION
[0002] Esters have been used as lubricating oils for over 50 years.
They are used in a variety of applications ranging from jet
engines, refrigeration and motor oils. In fact, esters were the
first synthetic crankcase motor oils in automotive applications.
However, esters gave way to polyalphaolefins (PAOs) due to the
lower cost of PAOs and their formulation similarities to mineral
oils. In full synthetic motor oils, however, esters are almost
always used in combination with PAOs to balance the effect on
seals, additives solubility, volatility reduction, and energy
efficiency improvement by enhanced lubricity. In this aspect, novel
diester-based multi-grade engine oil compositions comprising PAOs
have been described in commonly-assigned U.S. patent application
Ser. No. 12/548,191; filed Aug. 26, 2009.
[0003] Ester-based lubricants, in general, have excellent
lubrication properties due to the polarity of the ester molecules
of which they are comprised. The polar ester groups of such
molecules adhere to positively-charged metal surfaces creating
protective films which slow down the wear and tear of the metal
surfaces. Such lubricants are less volatile than the traditional
lubricants and tend to have much higher flash points and much lower
vapor pressures. Ester lubricants are excellent solvents and
dispersants, and can readily solvate and disperse the degradation
by-products of oils. Therefore, they greatly reduce sludge buildup.
While ester lubricants are stable to thermal and oxidative
processes, the ester functionalities give microbes a handle to do
their biodegrading more efficiently and more effectively than their
mineral oil-based analogues. Therefore, there exists an opportunity
to employ an alternative blending component that reduces volatility
at a reduced cost and with other advantages not afforded with
PAO.
[0004] In view of the foregoing, a simpler, more efficient method
of generating diester-based multi-grade engine oils would be
extremely useful, particularly wherein such methods utilize
renewable raw materials in combination with converting low value
Fischer-Tropsch (FT) olefins and alcohols to high value diester
base oils.
[0005] Novel diester-based lubricant compositions and their
corresponding syntheses have been described in commonly-assigned
U.S. Pat. No. 7,871,967 B2; issued Jan. 18, 2011. The synthetic
routes described in this patent application comprise and/or
generally proceed through the following sequence of reaction steps:
(1) epoxidation of an olefin to form an epoxide; (2) conversion of
the epoxide to form a diol; and (3) esterification of the diol to
form a diester.
[0006] Moreover, novel diester-based lubricant compositions and
their corresponding syntheses have been described in
commonly-assigned U.S. Pat. No. 7,867,959 B2; issued Jan. 11, 2011.
The synthetic routes described in this patent application comprise
and/or generally proceed through the following sequence of reaction
steps: (1) epoxidation of an olefin to form an epoxide; (2)
directly esterifying the epoxide with a carboxylic acid to form a
diester species.
[0007] Numerous governing organizations, including Original
Equipment Manufacturers (OEM's), the American Petroleum Institute
(API), Association des Consructeurs d' Automobiles (ACEA), the
American Society of Testing and Materials (ASTM), International
Lubricant Standardization and Approval Committee (ILSAC), and the
Society of Automotive Engineers (SAE), among others, define the
specifications for lubricating base oils and engine oils.
Increasingly, the specifications for engine oils are calling for
products with excellent low temperature properties, high oxidation
stability, and low volatility. Currently, only a small fraction of
the base oils manufactured today are able to meet these demanding
specifications.
[0008] Engine oils are finished crankcase lubricants intended for
use in automobile engines and diesel engines and consist of two
general components (i.e., a lubricating base oil and additives).
Lubricating base oil is the major constituent in these finished
lubricants and contributes significantly to the properties of the
engine oil. Accordingly, there is need for Multi-grade engine oils
formulated lubricating oils, which have improved low volatility,
excellent cold flow properties and improved fuel economy to meet
today's stringent performance requirements. The minimum
specifications for the various viscosity grades of engine oils is
established by SAE J300 standards as revised in January 2009.
SUMMARY OF THE INVENTION
[0009] In one embodiment, the present invention is directed to a
multi-grade engine oil comprising: a) a diester component,
comprising a quantity of at least one diester species having the
following Formula I:
##STR00001##
[0010] wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same
or independently selected from C.sub.2 to C.sub.17 hydrocarbon
groups;
[0011] b) a second base oil; and
[0012] c) an additive package,
[0013] wherein the second base is selected from the group
consisting of Group I base oil, Group II base oil or Group III base
oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a chart illustrates the Noack and CCS Viscosity of
the diesters of the present invention as compared to the current
commercial esters as presented in Table 6 and other Group II and
III bases oils.
DETAILED DESCRIPTION OF THE INVENTION
[0015] In some embodiments, the present invention is directed to a
multi-grade engine oil comprising: a) a diester component,
comprising a quantity of at least one diester species of Formula I,
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or
independently selected from C.sub.2 to C.sub.17 hydrocarbon groups;
b) a second base oil; and c) an additive package, wherein the
second base is selected from the group consisting of Group I base
oil, Group II base oil or Group III base oil.
[0016] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein a quantity of at least one diester
species comprises a mixture of isomers where R.sub.1 and R.sub.2
are different for each isomer.
[0017] In some embodiments, the present invention is directed to a
multi-grade engine oil, further comprising, a third base oil.
[0018] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the diester has a Noack Volatility
between about 6 and 10 wt %, a CCS Viscosity at -30.degree. C.
between about 700 and 2000 cP, a pour point less than about
-10.degree. C., a cloud point less than about -10.degree. C., a
kinematic viscosity at 100.degree. C. between about 2.5 to 6.5
centistokes, a VI greater than about 110 and a BN Oxidator greater
than about 20 hours.
[0019] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the diester has a Noack Volatility
between about 6 and 9 wt %, and a CCS Viscosity at -30.degree. C.
between about 800 and 1900 cP.
[0020] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the diester has a Noack Volatility
between about 6 and 9 wt %, and a CCS Viscosity at -25.degree. C.
between about 400 and 1250 cP.
[0021] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the second base and third base oil
are independently selected from the group consisting of light
neutral base oil, medium neutral base oil, Yubase 4, Yubase 6,
150R, 600R, 110RLV, 220R and 100R.
[0022] In some embodiments, the present invention is directed to a
multi-grade engine oil, meeting the specifications for SAE
viscosity grade 0W-XX or 5W-XX, wherein XX represents the integer
16, 20, 30, or 40.
[0023] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the multi-grade engine oil meets
the SAE J300 standards as revised in January 2009.
[0024] In some embodiments, the present invention is directed to a
multi-grade engine oil, having: a) a viscosity index between about
140-200; b) a kinematic viscosity at 100.degree. C. between about
6-10 cSt; c) a Pour Point less than about -30.degree. C.; and d) a
Noack volatility of less than about 15 wt %, wherein the
multi-grade engine oil is a 0W-SAE grade with a CCS Viscosity at
-35.degree. C. less than about 6200 cP or the multi-grade engine
oil is a 5W-SAE grade with a CCS Viscosity at -30.degree. C. less
than about 6600 cP.
[0025] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the kinematic viscosity of the
multi-grade engine oil at a temperature of 100.degree. C. is
between about 3 to 10 centistokes.
[0026] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the CCS Viscosity at -30.degree. C.
less than about 6,600 cP.
[0027] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the CCS Viscosity at -35.degree. C.
less than about 6,200 cP.
[0028] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the Noack Volatility less than
about 15 wt %.
[0029] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein R.sub.1 and R.sub.2 are selected to
have a combined carbon number of from 6 to 16 and R.sub.3 and
R.sub.4 are selected to have a combined carbon number of from 10 to
34.
[0030] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein R.sub.1 and R.sub.2 of Formula I
are selected to have a combined carbon number of C.sub.16, C.sub.14
or C.sub.12 and R.sub.3 and R.sub.4 are independently selected from
the group consisting of C.sub.12 and a mixture of
C.sub.6-C.sub.10.
[0031] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the at least one diester species is
derived from a C.sub.8 to C.sub.18 olefin and a C.sub.6 to C.sub.14
carboxylic acid.
[0032] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein said composition comprises
quantities of at least two different diester isomers.
[0033] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the at least one diester species
has a molecular mass that is from at least about 340 a.m.u. to at
most about 780 a.m.u.
[0034] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the at least one diester species is
selected from the group consisting of decanoic acid
2-decanoyloxy-1-hexyl-octyl ester and its isomers, tetradecanoic
acid-1-hexyl-2-tetradecanoyloxy-octyl esters and its isomers,
dodecanoic acid 2-dodecanoyloxy-1-hexyl-octyl ester and its
isomers, hexanoic acid 2-hexanoyloxy-1-hexy-octyl ester and its
isomers, octanoic acid 2-octanoyloxy-1-hexyl-octyl ester and its
isomers, hexanoic acid 2-hexanoyloxy-1-pentyl-heptyl ester and
isomers, octanoic acid 2-octanoyloxy-1-pentyl-heptyl ester and
isomers, decanoic acid 2-decanoyloxy-1-pentyl-heptyl ester and
isomers, decanoic acid-2-cecanoyloxy-1-pentyl-heptyl ester and its
isomers, dodecanoic acid-2-dodecanoyloxy-1-pentyl-heptyl ester and
isomers, tetradecanoic acid 1-penty-2-tetradecanoyloxy-heptyl ester
and isomers, tetradecanoic acid 1-butyl-2-tetradecanoyloxy-hexy
ester and isomers, dodecanoic acid-1-butyl-2-dodecanoyloxy-hexyl
ester and isomers, decanoic acid 1-butyl-2-decanoyloxy-hexyl ester
and isomers, octanoic acid 1-butyl-2-octanoyloxy-hexyl ester and
isomers, hexanoic acid 1-butyl-2-hexanoyloxy-hexyl ester and
isomers, tetradecanoic acid 1-propyl-2-tetradecanoyloxy-pentyl
ester and isomers, dodecanoic acid 2-dodecanoyloxy-1-propyl-pentyl
ester and isomers, decanoic acid 2-decanoyloxy-1-propyl-pentyl
ester and isomers, octanoic acid 1-2-octanoyloxy-1-propyl-pentyl
ester and isomers, hexanoic acid 2-hexanoyloxy-1-propyl-pentyl
ester and isomers, and mixtures thereof.
[0035] In some embodiments, the present invention is directed to a
multi-grade engine oil, wherein the multi-grade engine oil is
formulated as a 0W-20 SAE 0W-16 or 5W-20 SAE engine oil.
I. Engine Oil Composition
[0036] Base oils are the most important component of lubricant
compositions, generally comprising greater than 70% of the
lubricant compositions. Lubricant compositions comprise a base oil
and at least one additive. Lubricant compositions can be used in
automobiles, diesel engines, axles, transmissions, and industrial
applications. Lubricant compositions must meet the specifications
for their intended application as defined by the concerned
governing organization.
[0037] Additives, which can be blended with the base oil, to
provide a lubricant composition include those which are intended to
improve select properties of the lubricant composition. Typical
additives include, for example, anti-wear additives, extreme
pressure agents, detergents (e.g., metal-containing detergents),
dispersants (e.g., ashless dispersants), antioxidants, pour point
depressants, VI Improvers (VII), viscosity modifiers, friction
modifiers, demulsifiers, antifoaming agents, inhibitors (e.g.,
corrosion inhibitors, rust inhibitors, etc.), seal swell agents,
emulsifiers, wetting agents, lubricity improvers, metal
deactivators, gelling agents, tackiness agents, bactericides,
fluid-loss additives, colorants, and the like. Additives can be
added in the form of an additive package, containing various
additives.
[0038] Dispersants:
[0039] Dispersants are generally used to maintain in suspension
insoluble materials resulting from oxidation during use, thus
preventing sludge flocculation and precipitation or deposition on
engine parts. Examples of dispersants include nitrogen-containing
ashless (metal-free) dispersants. An ashless dispersant generally
comprises an oil soluble polymeric hydrocarbon backbone having
functional groups that are capable of associating with particles to
be dispersed. Other examples of dispersants include, but are not
limited to, amines, alcohols, amides, or ester polar moieties
attached to the polymer backbones via bridging groups.
[0040] An ashless dispersant may be selected from oil soluble
salts, esters, amino-esters, amides, imides, and oxazolines of long
chain hydrocarbon substituted mono and dicarboxylic acids or their
anhydrides; thiocarboxylate derivatives of long chain hydrocarbons,
long chain aliphatic hydrocarbons having a polyamine attached
directly thereto; and Mannich condensation products formed by
condensing a long chain substituted phenol with formaldehyde and
polyalkylene polyamine Carboxylic dispersants are reaction products
of carboxylic acylating agents (acids, anhydrides, esters, etc.)
comprising at least 34 and preferably at least 54 carbon atoms with
nitrogen containing compounds (such as amines), organic hydroxy
compounds (such as aliphatic compounds including monohydric and
polyhydric alcohols, or aromatic compounds including phenols and
naphthols), and/or basic inorganic materials. These reaction
products include imides, amides, and esters, e.g., succinimide
dispersants.
[0041] Other suitable ashless dispersants may also include amine
dispersants, which are reaction products of relatively high
molecular weight aliphatic halides and amines, preferably
polyalkylene polyamines Other examples may further include "Mannich
dispersants," which are reaction products of alkyl phenols in which
the alkyl group contains at least 30 carbon atoms with aldehydes
(especially formaldehyde) and amines (especially polyalkylene
polyamines). Furthermore, ashless dispersants may even include
post-treated dispersants, which are obtained by reacting
carboxylic, amine or Mannich dispersants with reagents such as
dimercaptothiazoles, urea, thiourea, carbon disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides, nitrile epoxides, boron compounds and the like.
Suitable ashless dispersants may be polymeric, which are
interpolymers of oil-solubilizing monomers such as decyl
methacrylate, vinyl decyl ether and high molecular weight olefins
with monomers containing polar substitutes. Other suitable ashless
dispersants may also include an ethylene carbonate-treated
bissuccinimide derived from a polyisobutylene having a number
average molecular weight of about 2300 Daltons ("PIBSA 2300").
[0042] Viscosity Index Improvers (Modifiers):
[0043] The viscosity index of an engine oil base stock can be
increased, or improved, by incorporating therein certain polymeric
materials that function as viscosity modifiers (VM) or viscosity
index improvers (VII) in an amount of 0.3 to 25 wt %. of the final
weight of the engine oil. Examples include but are not limited to
olefin copolymers, such as ethylene-propylene copolymers,
styrene-isoprene copolymers, hydrated styrene-isoprene copolymers,
polybutene, polyisobutylene, polymethacrylates, vinylpyrrolidone
and methacrylate copolymers and dispersant type viscosity index
improvers. These viscosity modifiers can optionally be grafted with
grafting materials such as, for example, maleic anhydride, and the
grafted material can be reacted with, for example, amines, amides,
nitrogen-containing heterocyclic compounds or alcohol, to form
multifunctional viscosity modifiers (dispersant-viscosity
modifiers).
[0044] Other examples of viscosity modifiers include star polymers
(e.g., a star polymer comprising isoprene/styrene/isoprene
triblock). Yet other examples of viscosity modifiers include poly
alkyl(meth)acrylates of low Brookfield viscosity and high shear
stability, functionalized poly alkyl(meth)acrylates with dispersant
properties of high Brookfield viscosity and high shear stability,
polyisobutylene having a weight average molecular weight ranging
from 700 to 2,500 Daltons and mixtures thereof.
[0045] Friction Modifiers:
[0046] The lubricating oil composition may comprise at least a
friction modifier (e.g., a sulfur-containing molybdenum compound).
Certain sulfur-containing organo-molybdenum compounds are known to
modify friction in lubricating oil compositions, while also
offering antioxidant and antiwear credits. Examples of oil soluble
organo-molybdenum compounds include molybdenum succinimide complex,
dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates,
thioxanthates, sulfides, and the like, and mixtures thereof.
[0047] Other examples include at least a mono-, di- or triester of
a tertiary hydroxyl amine and a fatty acid as a friction modifying
fuel economy additive. Other examples are selected from the group
of succinamic acid, succinimide, and mixtures thereof. Other
examples are selected from an aliphatic fatty amine, an ether
amine, an alkoxylated aliphatic fatty amine, an alkoxylated ether
amine, an oil-soluble aliphatic carboxylic acid, a polyol ester, a
fatty acid amide, an imidazoline, a tertiary amine, a hydrocarbyl
succinic anhydride or acid reacted with an ammonia or a primary
amine, and mixtures thereof
[0048] Seal Swelling Agents:
[0049] Seal fixes are also termed seal swelling agents or seal
pacifiers. They are often employed in lubricant or additive
compositions to insure proper elastomer sealing, and prevent
premature seal failures and leakages. Seal swell agents may be
selected from oil-soluble, saturated, aliphatic, or aromatic
hydrocarbon esters such as di-2-ethylhexylphthalate, mineral oils
with aliphatic alcohols such as tridecyl alcohol, triphosphite
ester in combination with a hydrocarbonyl-substituted phenol, and
di-2-ethylhexylsebacate.
[0050] Corrosion Inhibitors (Anti-Corrosive Agents):
[0051] These additives are typically added to reduce the
degradation of the metallic parts contained in the engine oil in
amounts from about 0.02 to 1 wt %. Examples include zinc
dialkyldithiophosphate, phosphosulfurized hydrocarbons and the
products obtained by reaction of a phosphosulfurized hydrocarbon
with an alkaline earth metal oxide or hydroxide, preferably in the
presence of an alkylated phenol or of an alkylphenol thioester. The
rust inhibitor or anticorrosion agents may be a nonionic
polyoxyethylene surface active agent. Nonionic polyoxyethylene
surface active agents include, but are not limited to,
polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether,
polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl
ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl
ether, polyoxyethylene sorbitol monostearate, polyoxyethylene
sorbitol mono-oleate, and polyethylene glycol monooleate. Rust
inhibitors or anticorrosion agents may also be other compounds,
which include, for example, stearic acid and other fatty acids,
dicarboxylic acids, metal soaps, fatty acid amine salts, metal
salts of heavy sulfonic acid, partial carboxylic acid ester of
polyhydric alcohols, and phosphoric esters. The rust inhibitor may
be a calcium stearate salt.
[0052] Detergents:
[0053] In engine oil compositions, metal-containing or ash-forming
detergents function both as detergents to reduce or remove deposits
and as acid neutralizers or rust inhibitors, thereby reducing wear
and corrosion and extending engine life. Detergents generally
comprise a polar head with long hydrophobic tail, with the polar
head comprising a metal salt of an acid organic compound.
[0054] The engine oil composition may contain one or more
detergents, which are normally salts (e.g., overbased salts.
Overbased salts, or overbased materials), are single phase,
homogeneous Newtonian systems characterized by a metal content in
excess of that which would be present according to the
stoichiometry of the metal and the particular acidic organic
compound reacted with the metal. The engine oil composition may
comprise at least a carboxylate detergent. Carboxylate detergents,
e.g., salicylates, can be prepared by reacting an aromatic
carboxylic acid with an appropriate metal compound such as an oxide
or hydroxide. The engine oil composition may comprise at least an
overbased detergent. Examples of the overbased detergents include,
but are not limited to calcium sulfonates, calcium phenates,
calcium salicylates, calcium stearates and mixtures thereof.
Overbased detergents may be low overbased (e.g., Total Base Number
(TBN) below about 50). Suitable overbased detergents may
alternatively be high overbased (e.g., TBN above about 150) or
medium overbased (e.g., TBN between 50 and 150). The lubricating
oil compositions may comprise more than one overbased detergents,
which may be all low-TBN detergents, all high-TBN detergents, or a
mix of those two types. Other suitable detergents for the
lubricating oil compositions include "hybrid" detergents such as,
for example, phenate/salicylates, sulfonate/phenates,
sulfonate/salicylates, sulfonates/phenates/salicylates, and the
like. The composition may comprise detergents made from alkyl
benzene and fuming sulfonic acid, phenates (high overbased, medium
overbased, or low overbased), high overbased phenate stearates,
phenolates, salicylates, phosphonates, thiophosphonates,
sulfonates, carboxylates, ionic surfactants and sulfonates and the
like.
[0055] Oxidation Inhibitors/Antioxidants:
[0056] Oxidation inhibitors or antioxidants reduce the tendency of
mineral oils to deteriorate in service, which deterioration is
evidenced by the products of oxidation such as sludge, lacquer, and
varnish-like deposits on metal surfaces. The engine oil composition
may contain from about 50 ppm to about 5.00 wt % of at least an
antioxidant selected from the group of phenolic antioxidants,
aminic antioxidants, or a combination thereof. The amount of
antioxidants may be between 0.10 to 3.00 wt %. The amount of
antioxidants may be between about 0.20 to 0.80 wt %. An example of
an antioxidant used is di-C8-diphenylamine, in an amount of about
0.05 to 2.00 wt % of the total weight of the oil composition. Other
examples of antioxidants include MoS and Mo oxide compounds.
[0057] Other examples of antioxidants include hindered phenols;
alkaline earth metal salts of alkylphenolthioesters having C5 to
C12 alkyl side chains; calcium nonylphenol sulphide; oil soluble
phenates and sulfurized phenates; phosphosulfurized or sulfurized
hydrocarbons or esters; phosphorous esters; metal thiocarbamates;
oil soluble copper compounds known in the art; phenyl naphthyl
amines such as phenylene diamine, phenothiazine, diphenyl amine,
diarylamine; phenyl-alphanaphthylamine, 2,2'-diethyl-4,4'-dioctyl
diphenylamine, 2,2'diethyl-4-t-octyldiphenylamine; alkaline earth
metal salts of alkylphenol thioesters, having C5 to C12 alkyl side
chains, e.g., calcium nonylphenol sulfide, barium t-octylphenol
sulfide, zinc dialkylditbiophosphates, dioctylphenylamine,
phenylalphanaphthylamine and mixtures thereof. Some of these
antioxidants further function as corrosion inhibitors. Other
suitable antioxidants which also function as antiwear agents
include bis alkyl dithiothiadiazoles such as 2,5-bis-octyl
dithiothiadiazole.
[0058] Anti-Foamants:
[0059] The engine oil may comprise an anti-foamant (foam inhibitor)
in amounts ranging from about 5 to about 50 ppm. Examples include
alkyl methacrylate polymers, dimethyl silicone polymers, and foam
inhibitors of the polysiloxane type, e.g., silicone oil and
polydimethyl siloxane, for foam control. The anti-foamant may be a
mixture of polydimethyl siloxane and fluorosilicone. Another
example of an anti-foamant may be an acrylate polymer anti-foamant,
with a weight ratio of the fluorosilicone antifoamant to the
acrylate anti-foamant ranging from about 3:1 to about 1:4. Another
example of an anti-foamant may be an anti-foam-effective amount of
a silicon-containing anti-foamant such that the total amount of
silicon in the engine oil is at least 30 ppm. The
silicon-containing antifoam agent may be selected from the group
consisting of fluorosilicones, polydimethylsiloxane, phenyl-methyl
polysiloxane, linear siloxanes, cyclic siloxanes, branched
siloxanes, silicone polymers and copolymers, organo-silicone
copolymers, and mixtures thereof.
[0060] Anti-Wear Agents:
[0061] Anti-wear agents can also be added to the engine oil
composition. The composition may comprise at least an anti-wear
agent selected from phosphates, phosphites, carbamates, esters,
sulfur containing compounds, and molybdenum complexes. Other
representative of suitable antiwear agents are zinc
dialkyldithiophosphate, zinc diaryldilhiophosphate, Zn or Mo
dithiocarbamates, phosphites, amine phosphates, borated
succinimide, magnesium sulfonate, and mixtures thereof. The
composition may comprise at least a dihydrocarbyl dithiophosphate
metal as antiwear and antioxidant agent in amounts of about 0.1 to
about 10 wt %. The metal may be an alkali or alkaline earth metal,
or aluminum, lead, tin, molybdenum, manganese, nickel or
copper.
[0062] Extreme Pressure Agents:
[0063] The engine oil composition may comprise an extreme pressure
agent. Examples include alkaline earth metal borated extreme
pressure agents and alkali metal borated extreme pressure agents.
Other examples include sulfurized olefins, zinc
dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl
type), di-phenyl sulfide, methyl tri-chlorostearate, chlorinated
naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized
or partially neutralized phosphates, di-thiophosphates, and
sulfur-free phosphates.
[0064] Some of the above-mentioned additives can provide a
multiplicity of effects; thus for example, a single additive may
act as a dispersant as well as an oxidation inhibitor. These
multifunctional additives are well known. Furthermore, when the
engine oil composition contains one or more of the above-mentioned
additives, each additive is typically blended into the base oil in
an amount that enables the additive to provide its desired
function. It may be desirable, although not essential to prepare
one or more additive concentrates comprising additives
(concentrates sometimes being referred to as "additive packages")
whereby several additives can be added simultaneously to the oil to
form the end oil composition. The final composition may employ from
about 0.5 to about 30 wt % of the concentrate, the remainder being
the oil of lubricating viscosity. The components can be blended in
any order and can be blended as combinations of components.
DEFINITIONS AND TERMS
[0065] The following terms will be used throughout the
specification and will have the following meanings unless otherwise
indicated.
[0066] The phrase "Group I Base Oil" contain less than 90 percent
saturates and/or greater than 0.03 percent sulfur and have a
viscosity index greater than or equal to 80 and less than 120 using
the ASTM methods specified in Table E-1 of American Petroleum
Institute Publication 1509.
[0067] The term "Group II Base Oil" refers to a base oil which
contains greater than or equal to 90% saturates and less than or
equal to 0.03% sulfur and has a viscosity index greater than or
equal to 80 and less than 120 using the ASTM methods specified in
Table E-1 of American Petroleum Institute Publication 1509.
[0068] The term "Group II+ Base Oil" refers to a Group II base oil
having a viscosity index greater than or equal to 110 and less than
120.
[0069] The term "Group III Base Oil" refers to a base oil which
contains greater than or equal to 90% saturates and less than or
equal to 0.03% sulfur and has a viscosity index greater than or
equal to 120 using the ASTM methods specified in Table E-1 of
American Petroleum Institute Publication 1509.
[0070] The term "Fischer-Tropsch derived" means that the product,
fraction, or feed originates from or is produced at some stage by a
Fischer-Tropsch process.
[0071] The term "petroleum derived" means that the product,
fraction, or feed originates from the vapor overhead streams from
distilling petroleum crude and the residual fuels that are the
non-vaporizable remaining portion. A source of the petroleum
derived product, fraction, or feed can be from a gas field
condensate.
[0072] The term "multi-grade engine oil" refers to an engine oil
that has viscosity/temperature characteristics which fall within
the limits of two different SAE numbers in SAE J300. The present
invention is directed to the discovery that multi-grade engine oils
meeting the specifications under SAE J300 as revised 2009,
including the MRV viscosity specifications, may be prepared from
Fischer-Tropsch base oils having a defined cycloparaffin
functionality when they are blended with a pour point depressing
base oil blending component and an additive package.
[0073] The term "light neutral base oil" refers to a base oil with
a boiling range from about 700.degree. F. to about 800.degree. F.,
a kinematic viscosity at 100.degree. C. from 4 cSt to about 5
cSt.
[0074] The term "medium neutral base oil" refers to a base oil with
a boiling range from about 800.degree. F. to about 900.degree. F.,
a kinematic viscosity at 100.degree. C. from 5 cSt to about 8
cSt.
[0075] Highly paraffinic wax means a wax having a high content of
n-paraffins, generally greater than 40 wt %, but can be greater
than 50 wt %, or even greater than 75 wt %, and less than 100 wt %
or 99 wt %. Examples of highly paraffinic waxes include slack
waxes, deoiled slack waxes, refined foots oils, waxy lubricant
raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical
plant processes, deoiled petroleum derived waxes, microcrystalline
waxes, Fischer-Tropsch waxes, and mixtures thereof.
[0076] The term "derived from highly paraffinic wax" means that the
product, fraction, or feed originates from or is produced at some
stage by from a highly paraffinic wax.
[0077] Aromatics means any hydrocarbonaceous compounds that contain
at least one group of atoms that share an uninterrupted cloud of
delocalized electrons, where the number of delocalized electrons in
the group of atoms corresponds to a solution to the Huckel rule of
4n+2 (e.g., n=1 for 6 electrons, etc.). Representative examples
include, but are not limited to, benzene, biphenyl, naphthalene,
and the like.
[0078] Molecules with cycloparaffinic functionality mean any
molecule that is, or contains as one or more substituents, a
monocyclic or a fused multicyclic saturated hydrocarbon group. The
cycloparaffinic group can be optionally substituted with one or
more, such as one to three, substituents. Representative examples
include, but are not limited to, cyclopropyl, cyclobutyl,
cyclohexyl, cyclopentyl, cycloheptyl, decahydronaphthalene,
octahydropentalene, (pentadecan-6-yl)cyclohexane,
3,7,10-tricyclohexylpentadecane,
decahydro-1-(pentadecan-6-yl)naphthalene, and the like.
[0079] Molecules with monocycloparaffinic functionality mean any
molecule that is a monocyclic saturated hydrocarbon group of three
to seven ring carbons or any molecule that is substituted with a
single monocyclic saturated hydrocarbon group of three to seven
ring carbons. The cycloparaffinic group can be optionally
substituted with one or more, such as one to three, substituents.
Representative examples include, but are not limited to,
cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl,
(pentadecan-6-yl)cyclohexane, and the like.
[0080] Molecules with multicycloparaffinic functionality mean any
molecule that is a fused multicyclic saturated hydrocarbon ring
group of two or more fused rings, any molecule that is substituted
with one or more fused multicyclic saturated hydrocarbon ring
groups of two or more fused rings, or any molecule that is
substituted with more than one monocyclic saturated hydrocarbon
group of three to seven ring carbons. The fused multicyclic
saturated hydrocarbon ring group often is of two fused rings. The
cycloparaffinic group can be optionally substituted with one or
more, such as one to three, substituents. Representative examples
include, but are not limited to, decahydronaphthalene,
octahydropentalene, 3,7,10-tricyclohexylpentadecane,
decahydro-1-(pentadecan-6-yl)naphthalene, and the like.
[0081] Brookfield Viscosity: ASTM D2983-04a is used to determine
the low-shear-rate viscosity of automotive fluid lubricants at low
temperatures. The low-temperature, low-shear-rate viscosity of
automatic transmission fluids, gear oils, torque and tractor
fluids, and industrial and automotive hydraulic oils are frequently
specified by Brookfield viscosities.
[0082] Kinematic viscosity is a measurement of the resistance to
flow of a fluid under gravity. Many base oils, lubricant
compositions made from them, and the correct operation of equipment
depends upon the appropriate viscosity of the fluid being used.
Kinematic viscosity is determined by ASTM D445-06. The results are
reported in mm.sup.2/s.
[0083] Viscosity index (VI) is an empirical, unitless number
indicating the effect of temperature change on the kinematic
viscosity of the oil. Viscosity index is determined by ASTM
D2270-04.
[0084] Pour point is a measurement of the temperature at which a
sample of base oil will begin to flow under carefully controlled
conditions. Pour point can be determined as described in ASTM
D5950-02. The results are reported in degrees Celsius. Many
commercial base oils have specifications for pour point. When base
oils have low pour points, the base oils are also likely to have
other good low temperature properties, such as low cloud point, low
cold filter plugging point, and low temperature cranking
viscosity.
[0085] Noack volatility is usually tested according to ASTM
D5800-05 Procedure B. A more convenient method for calculating
Noack volatility and one which correlates well with ASTM D5800-05
is by using a thermogravimetric analyzer (TGA) test by ASTM
D6375-05. TGA Noack volatility is used throughout the present
disclosure unless otherwise stated.
[0086] The base oils of the lubricant composition as disclosed
herein also have excellent viscometric properties under low
temperature (i.e., cold flow properties) and high shear, making
them very useful in multi-grade engine oils. The cold-cranking
simulator apparent viscosity (CCS VIS) is a test used to measure
the viscometric properties of base oils under low temperature and
high shear. The test method to determine CCS VIS is ASTM D5293-02.
Results are reported in mPas. CCS VIS has been found to correlate
with low temperature engine cranking. Specifications for maximum
CCS VIS are defined for automotive engine oils by SAE J300, revised
in 2009. The maximum CCS VIS for a 0W SAE Viscosity Grade engine
oil is 6200 mPas at -35.degree. C.
[0087] The phrase "improving cold flow properties" refers to one or
more of lowering CCS VIS (cold-cranking simulator apparent
viscosity) at -25.degree. C., -30.degree. C. or -35.degree. C.,
lowering pour point and lowering Noack.
[0088] The Mini-Rotary Viscometer (MRV) test, ASTM D4684-07, which
is related to the mechanism of pumpability, is a low shear rate
measurement. Slow sample cooling rate is the method's key feature.
A sample is pretreated to have a specified thermal history which
includes warming, slow cooling, and soaking cycles. The MRV
measures an apparent yield stress, which, if greater than a
threshold value, indicates a potential air-binding pumping failure
problem. Above a certain viscosity (currently defined as 60,000
mPas by SAE J300 2009), the oil may be subject to pumpability
failure by a mechanism called "flow limited" behavior. An SAE 0W
oil, for example, is required to have a maximum viscosity of 60,000
mPas at -40.degree. C. with no yield stress. This method also
measures an apparent viscosity under shear rates of 1 to 50
s.sup.-1.
[0089] High temperature high shear rate viscosity (HTHS) is a
measure of a fluid's resistance to flow under conditions resembling
highly-loaded journal bearings in fired internal combustion
engines, typically 1 million s.sup.-1 at 150.degree. C. HTHS is a
better indication of how an engine operates at high temperature
with a given lubricant than the kinematic low shear rate
viscosities at 100.degree. C. The HTHS value directly correlates to
the oil film thickness in a bearing. SAE J300 2009 contains the
current specifications for HTHS measured by ASTM D4683, ASTM D4741,
or ASTM D5481. An SAE 20 viscosity grade engine oil, for example,
is required to have a minimum HTHS of 2.6 mPas.
[0090] Scanning Brookfield Viscosity: ASTM D5133-05 is used to
measure the low temperature, low shear rate, viscosity/temperature
dependence of engine oils. The low temperature, low shear
viscometric behavior of an engine oil determines whether the oil
will flow to the sump inlet screen, then to the oil pump, then to
the sites in the engine requiring lubrication in sufficient
quantity to prevent engine damage immediately or ultimately after
cold temperature starting. ASTM D5133-05, the Scanning Brookfield
Viscosity technique, measures the Brookfield viscosity of a sample
as it is cooled at a constant rate of 1.degree. C./hour. Like the
MRV, ASTM D5133-05 is intended to relate to the pumpability of an
oil at low temperatures. The test reports the gelation point,
defined as the temperature at which the sample reaches 30,000 mPas.
The gelation index is also reported, and is defined as the largest
rate of change of viscosity increase from -5.degree. C. to the
lowest test temperature. The latest API SM/ILSAC GF-4
specifications for passenger car engine oils require a maximum
gelation index of 12.
[0091] "Lubricants," as defined herein, are substances (usually a
fluid under operating conditions) introduced between two moving
surfaces so to reduce the friction and wear between them. Base oils
used as motor oils are generally classified by the American
Petroleum Institute as being mineral oils (Group I, II, and III) or
synthetic oils (Group IV and V). See American Petroleum Institute
(API) Publication Number 1509.
[0092] "Pour point," as defined herein, represents the lowest
temperature at which a fluid will pour or flow. See, e.g., ASTM
International Standard Test Methods D 5950-96, D 6892-03, and D
97.
[0093] "Cloud point," as defined herein, represents the temperature
at which a fluid begins to phase separate due to crystal formation.
See, e.g., ASTM Standard Test Methods D 5773-95, D 2500, D 5551,
and D 5771.
[0094] "Centistoke," abbreviated "cSt," is a unit for kinematic
viscosity of a fluid (e.g., a lubricant), wherein 1 centistoke
equals 1 millimeter squared per second (1 cSt=1 mm.sup.2/s). See,
e.g., ASTM Standard Guide and Test Methods D 2270-04, D 445-06, D
6074, and D 2983.
[0095] With respect to describing molecules and/or molecular
fragments herein, "R.sub.n," where "n" is an index, refers to a
hydrocarbon group, wherein the molecules and/or molecular fragments
can be linear and/or branched.
[0096] As defined herein, "C.sub.n," where "n" is an integer,
describes a hydrocarbon molecule or fragment (e.g., an alkyl group)
wherein "n" denotes the number of carbon atoms in the fragment or
molecule.
[0097] The prefix "bio," as used herein, refers to an association
with a renewable resource of biological origin, such as resource
generally being exclusive of fossil fuels.
[0098] The term "internal olefin," as used herein, refers to an
olefin (i.e., an alkene) having a non-terminal carbon-carbon double
bond (C.dbd.C). This is in contrast to ".alpha.-olefins" which do
bear a terminal carbon-carbon double bond.
[0099] The terms Yubase 4 and Yubase 6 are base oils defined as
presented in Table 1 shown below.
TABLE-US-00001 TABLE 1 Property Test Method YUBASE 4 YUBASE 6
Appearance Visual Bright & Clear Bright & Clear Specific
Gravity, ASTM D 1298 0.8338 0.8423 @15/4.degree. C. Kinematic
Viscosity, ASTM D 445 19.57 36.82 @40.degree. C. Kinematic
Viscosity, ASTM D 445 4.23 6.52 @100.degree. C. Viscosity Index
ASTM D 2270 122 131 Noack Volatility, wt % DIN 51581 15 7 Flash
Point, .degree. C. ASTM D 92 230 240 Pour Point, .degree. C. ASTM D
97 -15 -15 Color ASTM D 1500 L0.5 L0.5 Con. Carbon Residue, ASTM D
189 <0.01 <0.01 wt % Copper Corrosion ASTM D 130 1-a 1-a
Sulfur, ppm ASTM D 2622 <10 <10 Total Acid No., ASTM D 664
0.01 0.01 mgKOH/g
[0100] The terms "100R, 150R, 220R, 600R and 110RLV" are base oils
defined as presented in Table 2 shown below.
TABLE-US-00002 TABLE 2 Property ASTM Method 100R 150R 220R 600R
110RLV API Base Oil Category API 1509 E 1.3 II II II II II(+)
Appearance SM 360-99 Bright Bright Bright Bright Bright and Clear
and Clear and Clear and Clear and Clear Color ASTM D 1500 L0.5 L0.5
L0.5 L0.5 L0.5 API Gravity, deg. ASTM D 4052 34.4 33.4 31.9 31.2
35.4 Density, lb/gal ASTM D 4052 7.1 7.15 7.22 7.28 7.06 Density,
kg/l ASTM D 4052 0.853 0.858 0.867 0.874 0.848 Specific Gravity, @
ASTM D 4052 0.853 0.858 0.867 0.874 0.848 60.degree. F./60.degree.
F. Viscosity @ 40.degree. C., cSt ASTM D 445 20.3 30.9 43.7 108
21.1 Viscosity @ 100.degree. C., cSt ASTM D 445 4.1 5.3 6.6 12.2
4.4 Viscosity @ 100.degree. F., SUS ASTM D 2161 107 153 214 590 113
Viscosity Index ASTM D 2270 102 107 102 103 118 CCS @ -20.degree.
C., cP ASTM D 5293 N/A 1750 3400 N/A 822 CCS @ -25.degree. C., cP
ASTM D 5293 1400 2660 5600 N/A 1350 CCS @ -30.degree. C., cP ASTM D
5293 2650 5070 N/A N/A 2450 Pour Point, .degree. C. ASTM D 5950/1C
-15 -15 -13 -17 -15 Flash Point, COC, .degree. C. ASTM D 92 206 227
230 270 216 Volatility, wt. % distilled ASTM D 2887 13 N/A N/A N/A
N/A at 700.degree. F./371.degree. C. Evaporative Loss, ASTM D5800
(B) 26 14 10 2 16 NOACK, wt % Water, ppm ASTM D 6304-98 <50
<50 <50 <50 <50 Sulfur, ppm ICP/XRF <10 <10
<10 <10 <6 Saturates, HPLC wt. % Chevron >99 >99
>99 >99 >99 Aromatics, HPLC wt. % Chevron <1 <1
<1 <1 <1
[0101] Unless otherwise indicated herein, scientific and technical
terms used in connection with the present invention shall have the
meanings that are commonly understood by those of ordinary skill in
the art. Further, unless otherwise required by context, singular
terms shall include pluralities and plural terms shall include the
singular. More specifically, as used in this specification and the
appended claims, the singular forms "a", "an" and "the" include
plural referents unless the context clearly dictates otherwise.
Thus, for example, reference to "a fatty acid" includes a plurality
of fatty acids, and the like. In addition, ranges provided in the
specification and appended claims include both end points and all
points between the end points. Therefore, a range of 2.0 to 3.0
includes 2.0, 3.0 and all points between 2.0 and 3.0. Furthermore,
all numbers expressing quantities, percentages or proportions, and
other numerical values used in the specification and claims, are to
be understood as being modified in all instances by the term
"about". As used herein, the term "include" and its grammatical
variants are intended to be non-limiting, such that recitation of
items in a list is not to the exclusion of other like items that
can be substituted or added to the listed items. As used herein,
the term "comprising" means including elements or steps that are
identified following that term, but any such elements or steps are
not exhaustive, and an embodiment can include other elements or
steps.
EXAMPLES
[0102] The following examples are provided to demonstrate
particular embodiments of the present invention. It should be
appreciated by those of skill in the art that the methods disclosed
in the examples which follow merely represent exemplary embodiments
of the present invention. However, those of skill in the art
should, in light of the present disclosure, appreciate that many
changes can be made in the specific embodiments described and still
obtain a like or similar result without departing from the spirit
and scope of the present invention.
Example 1
[0103] This example serves to illustrate the base oil blends with
and without the diesters of the present invention with the
analytics presented in Table 3 below.
[0104] The diester-free base oil blend was prepared by mixing 82.67
wt % Yubase 4 and 17.33 wt % Yubase 6. The base oil component with
diester was prepared by mixing 69.7 wt % Yubase 4, 13.8 wt % Yubase
6, and 16.5 wt % diester of Formula I wherein R.sub.1 and R.sub.2
are combined to have a carbon number of C.sub.12 and R.sub.3 and
R.sub.4 are both C.sub.12. Both samples were submitted for standard
base oil testing, including API gravity, viscosity at 40.degree. C.
and 100.degree. C., Viscosity Index, pour point, cloud point, Noack
volatility, cold cranking viscosity, and Bromine number.
TABLE-US-00003 TABLE 3 Base Oil Blend Example 1 Diester A, wt % 0
16.5 Yubase 4, wt % 82.67 69.7 Yubase 6, wt % 17.33 13.8 Properties
API 42.5 36.2 Vis @ 100.degree. C., cSt 4.515 4.523 VI 130 132 Pour
point, .degree. C. -14 -17 Cloud point, .degree. C. -10 -12 Noack,
wt % 12.65 12.46 CCS @ -35.degree. C., cP 3225 2928 Bromine number
0.1 0.08
Example 2
[0105] This example serves to illustrate the base oil blends with
the diesters of the present invention, a single comparative without
diester and a second comparative with a commercially available
ester (i.e., Esterex A51) with the analytics presented in Table 4
below. Diester A is a diester of Formula I, wherein R.sub.1 and
R.sub.2 are combined to have a carbon number of C.sub.12 and
R.sub.3 and R.sub.4 are both C.sub.12. Diester B2 is a diester of
Formula I, wherein R.sub.1 and R.sub.2 are combined to have a
carbon number of C.sub.12 and R.sub.3 and R.sub.4 are both
independently C.sub.6-C.sub.10. The examples in Table 3 were
prepared in a similar manner as those of Example 1 herein.
TABLE-US-00004 TABLE 4 Composition, wt % BOB02958 BOB02959 BOB02960
BOB02961 110RLV 52.43 59.31 59.25 59.16 100R 13.01 220R 34.56 35.55
35.51 35.46 Diester A 5.14 Diester B2 5.24 Esterex A51 5.37 BOB
Properties, Calculated KV100, centistokes 4.988 5.07 5.044 5.103
KV40, centistokes 26.76 27.06 27.03 27.46 VI 112 115 114 115 CCS,
cP @ -25.degree. C. 2137 2103 2120 2164 CCS, cP @ -30.degree. C.
3929 3840 3880 3961 Noack volatility, % wt loss 14.8 BOB
Properties, Observed KV100, centistokes 4.971 5.002 4.975 5.047
KV40, centistokes 26.51 26.35 26.27 26.73 VI 113 117 115 117 CCS,
cP @ -25.degree. C. 2165 1952 1972 2084 CCS, cP @ -30.degree. C.
3912 3513 3529 3751 Noack, wt % 14.2 13.4 13.9 13.1
Example 3
[0106] This example serves to illustrate the diesters prepared and
their respective properties as presented in Table 5.
TABLE-US-00005 TABLE 5 Properties Starting Materials Cloud Pour
Viscosity Viscosity Viscosity Oxidator NOACK, No. Olefins Fatty
Acids Point Point (40.degree. C.) (100.degree. C.) Index BN wt %
loss A C14 C12 -28 -27 19.5 cSt 4.76 cSt 176 26 hrs 8.9 B B1 C14
C6(high)-C10 -69 -66 16.41 cSt 3.68 cSt 109 19.3 hrs.sup. -- B2 C14
C6(low)-C10 -60 -60 19.47 cSt 4.191 cSt 120 26.25 hrs 9.1 C C16 C12
-18 -19 24.44 cSt 5.218 cSt 152 38 hrs E C18 C6-C10 -24 -26 20.4
cSt 4.5 cSt 137 25.5 D D1 C16 C6(high)-C10 -51 -51 17.90 cSt 4.015
cSt 124 -- -- D2 C16 C6(low)-C10 -51 -53 21.54 cSt 4.545 cSt 128 26
hrs 6.3
Example 4
[0107] This example serves to illustrate the Noack and CCS
Viscosity of the diesters of the present invention as compared to
the current commercial esters and other Group II and III bases oils
as presented in Table 6 and FIG. 1.
TABLE-US-00006 TABLE 6 Sample CCS (-25) CCS (-30) Noack KV100
Diester A 542 812 8.9 4.76 Diester B2 1002 1717 9.1 4.19 Diester D2
1104 1875 6.3 4.545 Esterex A51 1468 2487 7.4 5.4 Esterex A32 212
319 30.3 2.8
[0108] All patents, patent applications and publications are herein
incorporated by reference to the same extent as if each individual
patent, patent application or publication was specifically and
individually indicated to be incorporated by reference.
[0109] The present invention if not to be limited in scope by the
specific embodiments described herein, which are intended as single
illustrations of individual aspects of the invention, and
functionally equivalent methods and components are within the scope
of the invention. Indeed, various modifications of the invention,
in addition to those shown and described herein will become
apparent to those skilled in the art from the foregoing description
and accompanying drawings. Such modifications are intended to fall
within the scope of the appended claims.
* * * * *