U.S. patent application number 16/021284 was filed with the patent office on 2019-01-03 for low viscosity engine oils containing isomerized phenolic-based detergents.
The applicant listed for this patent is CHEVRON JAPAN LTD., Chevron Oronite Company LLC. Invention is credited to Alexander Bowman Boffa, Curtis Bay Campbell, Koichi Kubo, Brendan P. Miller, John Robert Miller, Hitoshi Ohkubo, Isao Tanaka, Jacob Daniel Ward.
Application Number | 20190002784 16/021284 |
Document ID | / |
Family ID | 63080225 |
Filed Date | 2019-01-03 |
United States Patent
Application |
20190002784 |
Kind Code |
A1 |
Boffa; Alexander Bowman ; et
al. |
January 3, 2019 |
LOW VISCOSITY ENGINE OILS CONTAINING ISOMERIZED PHENOLIC-BASED
DETERGENTS
Abstract
This disclosure generally relates to a lubricating oil
composition having a HTHS viscosity at 150.degree. C. in a range of
about 1.3 to about 2.5 cP, comprising: (a) a major amount of an oil
of lubricating viscosity having a kinematic viscosity at
100.degree. C. in a range of 1.5 to 6.0 mm.sup.2/s; and (b) an
overbased metal salt of an alkyl-substituted detergent.
Inventors: |
Boffa; Alexander Bowman;
(Oakland, CA) ; Ward; Jacob Daniel; (Berkeley,
CA) ; Miller; Brendan P.; (Richmond, CA) ;
Tanaka; Isao; (Omaezaki City, JP) ; Ohkubo;
Hitoshi; (Omaezaki City, JP) ; Kubo; Koichi;
(Omaezaki City, JP) ; Miller; John Robert; (San
Rafael, CA) ; Campbell; Curtis Bay; (Hercules,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron Oronite Company LLC
CHEVRON JAPAN LTD. |
San Ramon
San Ramon |
CA
CA |
US
US |
|
|
Family ID: |
63080225 |
Appl. No.: |
16/021284 |
Filed: |
June 28, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62527119 |
Jun 30, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 135/10 20130101;
C10M 129/10 20130101; C10M 137/10 20130101; C10M 169/042 20130101;
C10M 145/14 20130101; C10N 2030/08 20130101; C10N 2030/04 20130101;
C10M 159/22 20130101; C10N 2020/071 20200501; C10N 2030/56
20200501; C10M 2207/044 20130101; C10N 2040/04 20130101; C10N
2030/02 20130101; C10M 2207/262 20130101; C10M 2209/084 20130101;
C10M 2223/045 20130101; C10N 2040/25 20130101 |
International
Class: |
C10M 129/10 20060101
C10M129/10; C10M 145/14 20060101 C10M145/14; C10M 135/10 20060101
C10M135/10; C10M 137/10 20060101 C10M137/10 |
Claims
1. A lubricating oil composition having a HTHS viscosity at
150.degree. C. in a range of about 1.3 to about 2.5 cP, comprising:
(a) a major amount of an oil of lubricating viscosity having a
kinematic viscosity at 100.degree. C. in a range of 1.5 to 6.0
mm.sup.2/s; and (b) an overbased metal salt of an alkyl-substituted
phenolic-based detergent, wherein the alkyl group is derived from
an isomerized normal alpha olefin having from about 10 to about 40
carbon atoms per molecule having an isomerization level (I) of the
normal alpha olefin of from about 0.1 to about 0.4.
2. The lubricating oil composition of claim 1, wherein the
alkyl-substituted phenolic-based detergent is selected from the
group consisting of a non-sulfur containing phenate,
sulfur-containing phenate, a naphthenate, a complex detergent, a
salixarate, a salicylate, a saligenin, a calixarene, sulfur-bridged
alkylphenols, alkylene-bridged alkylphenols, and mixtures
thereof.
3. The lubricating oil composition of claim 1 wherein the
alkyl-substituted phenolic-based detergent is a carboxylate or a
salicylate detergent, wherein the alkyl group is derived from an
isomerized alpha olefin having from about 10 to about 40 carbon
atoms per molecule having an isomerization level (I) of the normal
alpha olefin of from about 0.1 to 0.4.
4. The lubricating oil composition of claim 1 wherein the
alkyl-substituted phenolic-based detergent is an isomerized olefin
phenate detergent, wherein the alkyl group is derived from an
isomerized alpha olefin having from about 10 to about 40 carbon
atoms per molecule having an isomerization level (I) of the normal
alpha olefin of from about 0.1 to 0.4.
5. The lubricating oil composition of claim 1, wherein the
overbased metal salt is calcium, magnesium, or a combination
thereof.
6. The lubricating oil composition of claim 1, wherein the
lubricating oil composition is a 0W-8, 0W-12 or 0W-16 SAE viscosity
grade.
7. The lubricating oil composition of claim 1, wherein the oil of
lubricating viscosity is a base oil selected from one or more of
API Group II, Group III, Group IV, and Group V.
8. The lubricating oil composition of claim 1, wherein the
isomerized normal alpha olefin has an isomerization level (I) of
the normal alpha olefin of from about 0.12 to about 0.3.
9. The lubricating oil composition of claim 1, wherein the
isomerized normal alpha olefin has an isomerization level (I) of
the normal alpha olefin of about 0.16.
10. The lubricating oil composition of claim 1, wherein the
isomerized normal alpha olefin has an isomerization level (I) of
the normal alpha olefin of about 0.26.
11. The lubricating oil composition of claim 1, wherein the normal
alpha olefin mixture has from about 14 to about 28 carbon atoms per
molecule.
12. The overbased phenolic-based detergent of claim 1 wherein the
normal alpha olefin mixture has from about 18 to about 24 carbon
atoms per molecule.
13. The overbased phenolic-based detergent of claim 1 wherein the
normal alpha olefin mixture has from about 20 to about 24 carbon
atoms per molecule.
14. The lubricating oil composition of claim 1, wherein the TBN of
the detergent is from 100 to 600 mg KOH/gram on an oil free
basis.
15. The lubricating oil composition of claim 1, further comprising
an additional detergent selected from the group consisting of
sulfonate, phenate, and salicylate.
16. The lubricating oil composition of claim 15, wherein the
detergent is a magnesium sulfonate.
17. The lubricating oil composition of claim 1, further comprising
a polymethacrylate dispersant VII.
18. The lubricating oil composition of claim 1, further comprising
a primary or secondary zinc dithiophosphate compound or a mixture
thereof.
19. The lubricating oil composition of claim 1, further comprising
a friction modifier.
20. A method of lubricating an engine comprising lubricating said
engine with a lubricating oil composition having a HTHS viscosity
at 150.degree. C. in a range of about 1.3 to about 2.5 cP,
comprising: (a) a major amount of an oil of lubricating viscosity
having a kinematic viscosity at 100.degree. C. in a range of 1.5 to
6.0 mm.sup.2/s; and (b) an overbased metal salt of an
alkyl-substituted phenolic-based detergent, wherein the alkyl group
is derived from an isomerized normal alpha olefin having from about
10 to about 40 carbon atoms per molecule having an isomerization
level (I) of the normal alpha olefin of from about 0.1 to about
0.4.
Description
[0001] This application claims the benefit of and priority to U.S.
Provisional Application Ser. No. 62/527,119, filed Jun. 30,
2017.
BACKGROUND
[0002] Engine oil is blended with various additives in order to
satisfy various performance requirements. One well known way to
increase fuel economy is to decrease the viscosity of the
lubricating oil. However, this approach is now reaching the limits
of current equipment capabilities and specifications.
[0003] The boundary friction regime is an important consideration
in the design of low viscosity engine oils. Boundary friction
occurs when the fluid film separating two surfaces becomes thinner
than the height of asperities on the surfaces. The resulting
surface to surface contact creates undesirable high friction and
poor fuel economy in an engine. Boundary friction in an engine can
occur under high loads, low engine speeds and at low oil
viscosities. Low viscosity engine oils make the engine more
susceptible to operating in boundary friction conditions due to the
oil's thinner, less robust film. Because additives--not base
oil--influence the coefficient of friction under boundary
conditions, additives that demonstrate lower coefficients of
friction under boundary conditions will give superior fuel economy
in a low viscosity oil in an engine (i.e., less than 20 SAE grade).
Second, it is also of high importance to have additives with
superior low temperature performance to meet the demands of a 0W-XX
lubricating oil which have more severe low temperature pumping and
cranking requirements.
[0004] Despite the advances in lubricant oil formulation
technology, there exists a need for a low viscosity engine oil
lubricant possessing the benefits described above.
SUMMARY OF THE DISCLOSURE
[0005] This disclosure generally relates to a lubricating oil
composition having a HTHS viscosity at 150.degree. C. in a range of
about 1.3 to about 2.5 cP, comprising: (a) a major amount of an oil
of lubricating viscosity having a kinematic viscosity at
100.degree. C. in a range of 1.5 to 6.0 mm.sup.2/s; and (b) an
overbased metal salt of an alkyl-substituted detergent.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0006] To facilitate the understanding of the subject matter
disclosed herein, a number of terms, abbreviations or other
shorthand as used herein are defined below. Any term, abbreviation
or shorthand not defined is understood to have the ordinary meaning
used by a skilled artisan contemporaneous with the submission of
this application.
Definitions
[0007] In this specification, the following words and expressions,
if and when used, have the meanings given below.
[0008] A "major amount" means in excess of 50 weight % of a
composition.
[0009] A "minor amount" means less than 50 weight % of a
composition, expressed in respect of the stated additive and in
respect of the total mass of all the additives present in the
composition, reckoned as active ingredient of the additive or
additives.
[0010] "Active ingredients" or "actives" refers to additive
material that is not diluent or solvent.
[0011] All percentages reported are weight % on an active
ingredient basis (i.e., without regard to carrier or diluent oil)
unless otherwise stated.
[0012] The term "phenate" means a salt of a phenol.
[0013] The abbreviation "ppm" means parts per million by weight,
based on the total weight of the lubricating oil composition.
[0014] Total base number (TBN) was determined in accordance with
ASTM D2896.
[0015] High temperature high shear (HTHS) viscosity at 150.degree.
C. was determined in accordance with ASTM D4683.
[0016] Kinematic viscosity at 100.degree. C. (KV.sub.100) was
determined in accordance with ASTM D445.
[0017] Cold Cranking Simulator (CCS) viscosity at -35.degree. C.
was determined in accordance with ASTM D5293.
[0018] Noack volatility was determined in accordance with ASTM
D5800.
[0019] Boron, calcium, magnesium, molybdenum, phosphorus, sulfur,
and zinc contents were determined in accordance with ASTM
D5185.
[0020] Nitrogen content was determined in accordance with ASTM
D4629.
[0021] Metal--The term "metal" refers to alkali metals, alkaline
earth metals, or mixtures thereof.
[0022] Olefins--The term "olefins" refers to a class of unsaturated
aliphatic hydrocarbons having one or more carbon-carbon double
bonds, obtained by a number of processes. Those containing one
double bond are called mono-alkenes, and those with two double
bonds are called dienes, alkyldienes, or diolefins. Alpha olefins
are particularly reactive because the double bond is between the
first and second carbons. Examples are 1-octene and 1-octadecene,
which are used as the starting point for medium-biodegradable
surfactants. Linear and branched olefins are also included in the
definition of olefins.
[0023] Normal Alpha Olefins--The term "Normal Alpha Olefins"
"refers to olefins which are straight chain, non-branched
hydrocarbons with carbon-carbon double bond present in the alpha or
primary position of the hydrocarbon chain.
[0024] Isomerized Normal Alpha Olefin. The term "Isomerized Normal
Alpha Olefin" as used herein refers to an alpha olefin that has
been subjected to isomerization conditions which results in an
alteration of the distribution of the olefin species present and/or
the introduction of branching along the alkyl chain. The isomerized
olefin product may be obtained by isomerizing a linear alpha olefin
containing from about 10 to about 40 carbon atoms, preferably from
about 20 to about 28 carbon atoms, and preferably from about 20 to
about 24 carbon atoms.
[0025] C.sub.10-40 Normal Alpha Olefins--This term defines a
fraction of normal alpha olefins wherein the carbon numbers below
10 have been removed by distillation or other fractionation
methods.
[0026] All ASTM standards referred to herein are the most current
versions as of the filing date of the present application.
[0027] In an aspect, provided is a lubricating oil composition
having a HTHS viscosity at 150.degree. C. in a range of about 1.3
to about 2.5 cP, comprising: [0028] (a) a major amount of an oil of
lubricating viscosity having a kinematic viscosity at 100.degree.
C. in a range of 1.5 to 6.0 mm.sup.2/s; and [0029] (b) an overbased
metal salt of an alkyl-substituted phenolic-based detergent, [0030]
wherein the alkyl group is derived from an isomerized alpha olefin
having from about 10 to about 40 carbon atoms per molecule, having
an isomerization level (I) of the normal alpha olefin of from about
0.1 to about 0.4.
[0031] In one embodiment, the metal salt is calcium, magnesium, or
combinations thereof.
[0032] In one embodiment, provided is a lubricating oil composition
having a HTHS viscosity at 150.degree. C. in a range of about 1.3
to about 2.5 cP, comprising: [0033] (a) a major amount of an oil of
lubricating viscosity having a kinematic viscosity at 100.degree.
C. in a range of 1.5 to 6.0 mm.sup.2/s; and [0034] (b) an overbased
metal salt of an alkyl-substituted phenolic-based detergent, [0035]
wherein the alkyl group is derived from an isomerized alpha olefin
having from about 10 to about 40 carbon atoms per molecule having
an isomerization level (I) of the normal alpha olefin of from about
0.1 to about 0.4, and wherein the alkyl-substituted phenolic-based
detergent is selected from the group consisting of a non-sulfur
containing phenate, sulfur-containing phenate, a naphthenate, a
complex detergent, a salixarate, a carboxylate, a salicylate, a
saligenin, a calixarene, sulfur-bridged alkylphenols,
alkylene-bridged alkylphenols, and mixtures thereof.
[0036] In one embodiment, the metal salt is calcium, magnesium, or
combinations thereof.
[0037] In an embodiment, provided is a lubricating oil composition
having a HTHS viscosity at 150.degree. C. in a range of about 1.3
to about 2.5 cP, comprising: [0038] (a) a major amount of an oil of
lubricating viscosity having a kinematic viscosity at 100.degree.
C. in a range of 1.5 to 6.0 mm.sup.2/s; and [0039] (b) an
alkyl-substituted phenolic-based detergent wherein the
phenolic-based detergent is a carboxylate or a salicylate
detergent, wherein [0040] the alkyl group is derived from an
isomerized alpha olefin having from about 10 to about 40 carbon
atoms per molecule having an isomerization level (I) of the normal
alpha olefin of from about 0.1 to about 0.4.
Phenolic-Based Alkylhydroxybenzoate Detergent
[0041] In one aspect of the present disclosure, the phenolic-based
alkylhydroxybenzoate detergent is an isomerized olefin
alkylhydroxybenzoate detergent.
[0042] In one aspect of the present disclosure, the TBN of the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO is 100-700, 100-650, 100-600, 100-500, 100-400,
100-300, 150-250, 175-250, 175-225 mg KOH/gram on oil
free-basis.
[0043] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent is derived from C.sub.10-C.sub.40
isomerized NAO and has a TBN of from 10 to 300, preferably from 50
to 300, more preferably from 100 to 300, even more preferably from
150 to 300, and most preferably from 175 to 250 mgKOH/gram on
active basis.
[0044] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO is a Ca alkylhydroxybenzoate detergent.
[0045] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent derived from C.sub.10-C.sub.40
isomerized NAO can be an alkylated hydroxybenzoate detergent. In
another embodiment, the detergent can be a salicylate detergent. In
another embodiment, the detergent can be a carboxylate
detergent.
[0046] In one aspect of the present disclosure, the
alkylhydroxybenzoate derived from C.sub.10-C.sub.40 isomerized NAO
may be prepared as described in U.S. Pat. No. 8,993,499 which is
herein incorporated in its entirety.
[0047] In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent is made from an alkylphenol having
an alkyl group derived from an isomerized alpha olefin having from
about 14 to about 28 carbon atoms per molecule, preferably from
about 20 to about 24 carbon atoms, or preferably from about 14 to
about 18 carbon atoms, or preferably from about 20 to about 28
carbon atoms per molecule.
[0048] In one aspect of the present disclosure, the
alkylhydroxybenzoate derived from C.sub.10-C.sub.40 isomerized NAO
is made from an alkylphenol with an alkyl group derived from an
isomerized NAO having an isomerization level (I) from about 0.10 to
about 0.40, preferably from about 0.10 to about 0.35, preferably
from about 0.10 to about 0.30, preferably from about 0.12 to about
0.30. and more preferably from about 0.12 to about 0.20.
[0049] In one aspect of the present disclosure, the
alkylhydroxybenzoate derived from C.sub.10-C.sub.40 isomerized NAO
is made from one or more alkylphenols with an alkyl group derived
from C.sub.10-C.sub.40 isomerized NAO and one or more alkylphenols
with an alkyl group different from C.sub.10-C.sub.40 isomerized
NAO.
[0050] In one aspect of the present disclosure, the isomerized NAO
of the alkylhydroxybenzoate detergent has an isomerization level of
about 0.16, and have from about 20 to about 24 carbon atoms.
[0051] In one aspect of the present disclosure, the isomerized NAO
of the alkylhydroxybenzoate detergent has an isomerization level of
about 0.26, and have from about 20 to about 24 carbon atoms.
[0052] In one aspect of the present disclosure, the lubricating oil
composition comprises about 0.01 to 2.0 wt. % in terms of Ca
content of the alkylhydroxybenzoate derived from C.sub.10-C.sub.40
isomerized NAO, preferably 0.1 to 1.0 wt. %, more preferably 0.05
to 0.5 wt. %, more preferably 0.1 to 0.5 wt. %.
[0053] In one aspect of the present disclosure, the lubricating oil
composition comprising the alkylhydroxybenzoate detergent derived
from C.sub.10-C.sub.40 isomerized NAO is an automotive engine oil
composition, a gas engine oil composition, a dual fuel engine oil
composition, a mobile gas engine oil composition, or a locomotive
engine oil composition.
[0054] In one aspect of the present disclosure, the lubricating oil
composition comprising the alkylhydroxybenzoate detergent derived
from C.sub.10-C.sub.40 isomerized NAO is a functional fluid for
automotive and industrial applications, such as transmission oil,
hydraulic oil, tractor fluid, gear oil, and the like.
[0055] In one aspect of the present disclosure, the lubricating oil
composition comprising the alkylhydroxybenzoate detergent derived
from C.sub.10-C.sub.40 isomerized NAO is a multi-grade oil or
mono-grade oil.
[0056] In one aspect of the present disclosure, the lubricating oil
composition comprising the alkylhydroxybenzoate detergent derived
from C.sub.10-C.sub.40 isomerized NAO lubricates crankcases, gears,
as well as clutches.
Phenolic-Based Phenate Detergent
[0057] In one aspect of the present disclosure, the phenolic-based
detergent is an isomerized olefin phenate detergent.
[0058] In one aspect of the present disclosure, the isomerized
olefin phenate detergent has a TBN of 100-600, 150-500, 150-450,
200-450, 250-450, 300-450, 300-400, 325-425, 350-425, 350-400
mgKOH/gram on an oil free basis.
[0059] In one aspect of the present disclosure, the phenolic-based
detergent is an alkylated phenate detergent wherein the alkyl group
is derived from an isomerized normal alpha olefin having from about
10 to about 40 carbon atoms per molecule.
[0060] In one aspect of the present disclosure, the phenolic-based
detergent has an isomerization level (I) of the normal alpha olefin
is between from about 0.10 to about 0.40, preferably from about
0.10 to about 0.30, preferably from about 0.12 to about 0.30, and
more preferably from about 0.22 to about 0.30.
[0061] In one aspect of the present disclosure, the phenate
detergent is a sulfurized phenate detergent.
[0062] In one aspect of the present disclosure, the isomerized
olefin phenate detergent can be prepared as described in U.S. Pat.
No. 8,580,717 which is herein incorporated in its entirety.
[0063] In one aspect of the present disclosure, the alkyl group is
derived from an isomerized alpha olefin having from about 14 to
about 30, from about 16 to about 30, from about 18 to about 30,
from about 20 to about 28, 20 to about 24, or from about 18 to
about 28 carbon atoms per molecule.
[0064] In another embodiment, the isomerization level of the alpha
olefin is about 0.26, and having from about 20 to about 24 carbon
atoms.
Oil of Lubricating Viscosity
[0065] The oil of lubricating viscosity (sometimes referred to as
"base stock" or "base oil") is the primary liquid constituent of a
lubricant, into which additives and possibly other oils are
blended, for example to produce a final lubricant (or lubricant
composition). A base oil is useful for making concentrates as well
as for making lubricating oil compositions therefrom, and may be
selected from natural and synthetic lubricating oils and
combinations thereof.
[0066] Natural oils include animal and vegetable oils, liquid
petroleum oils and hydrorefined, solvent-treated mineral
lubricating oils of the paraffinic, naphthenic and mixed
paraffinic-naphthenic types. Oils of lubricating viscosity derived
from coal or shale are also useful base oils.
[0067] Synthetic lubricating oils include hydrocarbon oils such as
polymerized and interpolymerized olefins (e.g., polybutylenes,
polypropylenes, propylene-isobutylene copolymers, chlorinated
polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-decenes);
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di(2-ethylhexyl)benzenes; polyphenols (e.g.,
biphenyls, terphenyls, alkylated polyphenols); and alkylated
diphenyl ethers and alkylated diphenyl sulfides and the
derivatives, analogues and homologues thereof.
[0068] Another suitable class of synthetic lubricating oils
comprises the esters of dicarboxylic acids (e.g., malonic acid,
alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl
succinic acids and alkenyl succinic acids, maleic acid, fumaric
acid, azelaic acid, suberic acid, sebacic acid, adipic acid,
linoleic acid dimer, phthalic acid) with a variety of alcohols
(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether, propylene
glycol). Specific examples of these esters include dibutyl adipate,
di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic
acid dimer, and the complex ester formed by reacting one mole of
sebacic acid with two moles of tetraethylene glycol and two moles
of 2-ethylhexanoic acid.
[0069] Esters useful as synthetic oils also include those made from
C.sub.5 to C.sub.12 monocarboxylic acids and polyols, and polyol
ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol and tripentaerythritol.
[0070] The base oil may be derived from Fischer-Tropsch synthesized
hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made
from synthesis gas containing H.sub.2 and CO using a
Fischer-Tropsch catalyst. Such hydrocarbons typically require
further processing in order to be useful as the base oil. For
example, the hydrocarbons may be hydroisomerized; hydrocracked and
hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using
processes known to those skilled in the art.
[0071] Unrefined, refined and re-refined oils can be used in the
present lubricating oil composition. Unrefined oils are those
obtained directly from a natural or synthetic source without
further purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
directly from distillation or ester oil obtained directly from an
esterification process and used without further treatment would be
unrefined oil. Refined oils are similar to unrefined oils except
they have been further treated in one or more purification steps to
improve one or more properties. Many such purification techniques,
such as distillation, solvent extraction, acid or base extraction,
filtration and percolation are known to those skilled in the art.
Re-refined oils are obtained by processes similar to those used to
obtain refined oils applied to refined oils which have been already
used in service. Such re-refined oils are also known as reclaimed
or reprocessed oils and often are additionally processed by
techniques for approval of spent additive and oil breakdown
products.
[0072] Hence, the base oil which may be used to make the present
lubricating oil composition may be selected from any of the base
oils in Groups I-V as specified in the American Petroleum Institute
(API) Base Oil Interchangeability Guidelines (API Publication
1509). Such base oil groups are summarized in Table 1 below:
TABLE-US-00001 TABLE 1 Base Oil Properties Group.sup.(a)
Saturates.sup.(b), wt. % Sulfur.sup.(c), wt. % Viscosity
Index.sup.(d) Group I <90 and/or >0.03 80 to <120 Group II
.gtoreq.90 .ltoreq.0.03 80 to <120 Group III .gtoreq.90
.ltoreq.0.03 .gtoreq.120 Group IV Polyalphaolefins (PAOs) Group V
All other base stocks not included in Groups I, II, III or IV
.sup.(a)Groups I-III are mineral oil base stocks.
.sup.(b)Determined in accordance with ASTM D2007.
.sup.(c)Determined in accordance with ASTM D2622, ASTM D3120, ASTM
D4294 or ASTM D4927. .sup.(d)Determined in accordance with ASTM
D2270.
[0073] Base oils suitable for use herein are any of the variety
corresponding to API Group II, Group III, Group IV, and Group V
oils and combinations thereof, preferably the Group III to Group V
oils due to their exceptional volatility, stability, viscometric
and cleanliness features.
[0074] The base oil constitutes the major component of the present
lubricating oil composition and is present is an amount ranging
from greater than 50 to 99 wt. % (e.g., 70 to 95 wt. %, or 85 to 95
wt. %).
[0075] The base oil may be selected from any of the synthetic or
natural oils typically used as crankcase lubricating oils for
spark-ignited internal combustion engines. The base oil typically
has a kinematic viscosity at 100.degree. C. in a range of 1.5 to 6
mm.sup.2/s. In the case where the kinematic viscosity at
100.degree. C. of the lubricating base oil exceeds 6 mm.sup.2/s,
low temperature viscosity properties may be reduced, and sufficient
fuel efficiency may not be obtained. At a kinematic viscosity of
1.5 mm.sup.2/s or less, formation of an oil film in a lubrication
place is insufficient; for this reason, lubrication is inferior,
and the evaporation loss of the lubricating oil composition may be
increased.
[0076] Preferably, the base oil has a viscosity index of at least
90 (e.g., at least 95, at least 105, at least 110, at least 115, or
at least 120). If the viscosity index is less than 90, not only
viscosity-temperature properties, heat and oxidation stability, and
anti-volatilization are reduced, but also the coefficient of
friction tends to be increased; and resistance against wear tends
to be reduced.
Lubricating Oil Composition
[0077] The lubricating oil composition may be a multi-grade oil
identified by the viscosity grade descriptor SAE 0W-X, wherein X
represents any one of 8, 12, and 16.
[0078] The lubricating oil composition has a high temperature shear
(HTHS) viscosity at 150.degree. C. of 2.3 cP or less (e.g., 1.0 to
2.6 cP, or 1.3 to 2.3 cP), such as 2.0 cP or less (e.g., 1.0 to 2.0
cP, or 1.3 to 2.3 cP), or even 1.7 cP or less (e.g., 1.0 to 1.7 cP,
or 1.3 to 1.7 cP).
[0079] The lubricating oil composition has a viscosity index of at
least 135 (e.g., 135 to 400, or 135 to 250), at least 150 (e.g.,
150 to 400, 150 to 250), at least 165 (e.g., 165 to 400, or 165 to
250), at least 190 (e.g., 190 to 400, or 190 to 250), or at least
200 (e.g., 200 to 400, or 200 to 250). If the viscosity index of
the lubricating oil composition is less than 135, it may be
difficult to improve fuel efficiency while maintaining the HTHS
viscosity at 150.degree. C. If the viscosity index of the
lubricating oil composition exceeds 400, evaporation properties may
be reduced, and deficits due to insufficient solubility of the
additive and matching properties with a seal material may be
caused.
[0080] The lubricating oil composition has a kinematic viscosity at
100.degree. C. in a range of 3 to 12 mm.sup.2/s (e.g., 3 to 8.2
mm.sup.2/s, 3.5 to 8.2 mm.sup.2/s, or 4 to 8.2 mm.sup.2/s).
[0081] In general, the level of sulfur in the lubricating oil
compositions of the present invention is less than or equal to
about 0.7 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of sulfur of about 0.01 wt. % to about
0.70 wt. %, 0.01 to 0.6 wt. %, 0.01 to 0.5 wt. %, 0.01 to 0.4 wt.
%, 0.01 to 0.3 wt. %, 0.01 to 0.2 wt. %, 0.01 wt. % to 0.10 wt. %.
In one embodiment, the level of sulfur in the lubricating oil
compositions of the present invention is less than or equal to
about 0.60 wt. %, less than or equal to about 0.50 wt. %, less than
or equal to about 0.40 wt. %, less than or equal to about 0.30 wt.
%, less than or equal to about 0.20 wt. %, less than or equal to
about 0.10 wt. % based on the total weight of the lubricating oil
composition.
[0082] In one embodiment, the levels of phosphorus in the
lubricating oil compositions of the present invention is less than
or equal to about 0.12 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of
phosphorus in the lubricating oil compositions of the present
invention is less than or equal to about 0.11 wt. %, based on the
total weight of the lubricating oil composition, e.g., a level of
phosphorus of about 0.01 wt. % to about 0.11 wt. %. In one
embodiment, the levels of phosphorus in the lubricating oil
compositions of the present invention is less than or equal to
about 0.10 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to
about 0.10 wt. %. In one embodiment, the levels of phosphorus in
the lubricating oil compositions of the present invention is less
than or equal to about 0.09 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.09 wt. %. In one embodiment, the levels of
phosphorus in the lubricating oil compositions of the present
invention is less than or equal to about 0.08 wt. %, based on the
total weight of the lubricating oil composition, e.g., a level of
phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one
embodiment, the levels of phosphorus in the lubricating oil
compositions of the present invention is less than or equal to
about 0.07 wt. %, based on the total weight of the lubricating oil
composition, e.g., a level of phosphorus of about 0.01 wt. % to
about 0.07 wt. %. In one embodiment, the levels of phosphorus in
the lubricating oil compositions of the present invention is less
than or equal to about 0.05 wt. %, based on the total weight of the
lubricating oil composition, e.g., a level of phosphorus of about
0.01 wt. % to about 0.05 wt. %.
[0083] In one embodiment, the level of sulfated ash produced by the
lubricating oil compositions of the present invention is less than
or equal to about 1.60 wt. % as determined by ASTM D 874, e.g., a
level of sulfated ash of from about 0.10 to about 1.60 wt. % as
determined by ASTM D 874. In one embodiment, the level of sulfated
ash produced by the lubricating oil compositions of the present
invention is less than or equal to about 1.00 wt. % as determined
by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to
about 1.00 wt. % as determined by ASTM D 874. In one embodiment,
the level of sulfated ash produced by the lubricating oil
compositions of the present invention is less than or equal to
about 0.80 wt. % as determined by ASTM D 874, e.g., a level of
sulfated ash of from about 0.10 to about 0.80 wt. % as determined
by ASTM D 874. In one embodiment, the level of sulfated ash
produced by the lubricating oil compositions of the present
invention is less than or equal to about 0.60 wt. % as determined
by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to
about 0.60 wt. % as determined by ASTM D 874.
[0084] Suitably, the present lubricating oil composition may have a
total base number (TBN) of 4 to 15 mg KOH/g (e.g., 5 to 12 mg
KOH/g, 6 to 12 mg KOH/g, or 8 to 12 mg KOH/g).
Viscosity Modifier
[0085] The lubricating oil composition may also include a viscosity
modifier. Viscosity modifiers function to impart high and low
temperature operability to a lubricating oil. The viscosity
modifier used may have that sole function, or may be
multifunctional. Multifunctional viscosity modifiers that also
function as dispersants are also known. Suitable viscosity
modifiers include polyisobutylene, copolymers of ethylene and
propylene and higher alpha-olefins, polymethacrylates,
polyalkylmethacrylates, methacrylate copolymers, copolymers of an
unsaturated dicarboxylic acid and a vinyl compound, interpolymers
of styrene and acrylic esters, and partially hydrogenated
copolymers of styrene/isoprene, styrene/butadiene, and
isoprene/butadiene, as well as the partially hydrogenated
homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
In one embodiment, the viscosity modifier is a
polyalkylmethacrylate. The topology of the viscosity modifier could
include, but is not limited to, linear, branched, hyperbranched,
star, or comb topology.
[0086] Suitable viscosity modifiers have a Permanent Shear
Stability Index (PSSI) of 30 or less (e.g., 10 or less, 5 or less,
or even 2 or less). PSSI is a measure of the irreversible decrease,
resulting from shear, in an oil's viscosity contributed by an
additive. PSSI is determined according to ASTM D6022. The
lubricating oil compositions of the present disclosure display
stay-in-grade capability. Retention of kinematic viscosity at
100.degree. C. within a single SAE viscosity grade classification
by a fresh oil and its sheared version is evidence of an oil's
stay-in-grade capability.
[0087] The viscosity modifier may be used in an amount of from 0.5
to 15.0 wt. % (e.g., 0.5 to 10 wt. %, 0.5 to 5 wt. %, 1.0 to 15 wt.
%, 1.0 to 10 wt. %, or 1.0 to 5 wt. %), based on the total weight
of the lubricating oil composition. In one embodiment, a viscosity
modifier is not present in the lubricating oil compositions
described herein.
Additional Lubricating Oil Additives
[0088] The lubricating oil compositions of the present disclosure
may also contain other conventional additives that can impart or
improve any desirable property of the lubricating oil composition
in which these additives are dispersed or dissolved. Any additive
known to a person of ordinary skill in the art may be used in the
lubricating oil compositions disclosed herein. Some suitable
additives have been described in Mortier et al., "Chemistry and
Technology of Lubricants", 2nd Edition, London, Springer, (1996);
and Leslie R. Rudnick, "Lubricant Additives: Chemistry and
Applications", New York, Marcel Dekker (2003), both of which are
incorporated herein by reference. For example, the lubricating oil
compositions can be blended with antioxidants, anti-wear agents,
detergents such as metal detergents, rust inhibitors, dehazing
agents, demulsifying agents, metal deactivating agents, friction
modifiers, pour point depressants, antifoaming agents, co-solvents,
corrosion-inhibitors, ashless dispersants, multifunctional agents,
dyes, extreme pressure agents and the like and mixtures thereof. A
variety of the additives are known and commercially available.
These additives, or their analogous compounds, can be employed for
the preparation of the lubricating oil compositions of the
disclosure by the usual blending procedures.
[0089] In the preparation of lubricating oil formulations it is
common practice to introduce the additives in the form of 10 to 100
wt. % active ingredient concentrates in hydrocarbon oil, e.g.
mineral lubricating oil, or other suitable solvent.
[0090] Usually these concentrates may be diluted with 3 to 100,
e.g., 5 to 40, parts by weight of lubricating oil per part by
weight of the additive package in forming finished lubricants, e.g.
crankcase motor oils. The purpose of concentrates, of course, is to
make the handling of the various materials less difficult and
awkward as well as to facilitate solution or dispersion in the
final blend.
[0091] Each of the foregoing additives, when used, is used at a
functionally effective amount to impart the desired properties to
the lubricant. Thus, for example, if an additive is a friction
modifier, a functionally effective amount of this friction modifier
would be an amount sufficient to impart the desired friction
modifying characteristics to the lubricant.
[0092] In general, the concentration of each of the additives in
the lubricating oil composition, when used, may range from about
0.001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 15
wt. %, or from about 0.1 wt. % to about 10 wt. %, from about 0.005
wt. % to about 5 wt. %, or from about 0.1 wt. % to about 2.5 wt. %,
based on the total weight of the lubricating oil composition.
Further, the total amount of the additives in the lubricating oil
composition may range from about 0.001 wt. % to about 20 wt. %,
from about 0.01 wt. % to about 10 wt. %, or from about 0.1 wt. % to
about 5 wt. %, based on the total weight of the lubricating oil
composition.
[0093] The following examples are presented to exemplify
embodiments of the disclosure but are not intended to limit the
disclosure to the specific embodiments set forth. Unless indicated
to the contrary, all parts and percentages are by weight. All
numerical values are approximate. When numerical ranges are given,
it should be understood that embodiments outside the stated ranges
may still fall within the scope of the disclosure. Specific details
described in each example should not be construed as necessary
features of the disclosure. It will be understood that various
modifications may be made to the embodiments disclosed herein.
Therefore the above description should not be construed as
limiting, but merely as exemplifications of preferred embodiments.
For example, the functions described above and implemented as the
best mode for operating the present disclosure are for illustration
purposes only. Other arrangements and methods may be implemented by
those skilled in the art without departing from the scope and
spirit of this disclosure. Moreover, those skilled in the art will
envision other modifications within the scope and spirit of the
claims appended hereto.
EXAMPLES
[0094] The following examples are intended for illustrative
purposes only and do not limit in any way the scope of the present
disclosure.
[0095] The isomerization level was measured by an NMR method.
[0096] Isomerization level (I) and NMR Method
[0097] The isomerization level (I) of the olefin was determined by
hydrogen-1 (1H) NMR. The NMR spectra were obtained on a Bruker
Ultrashield Plus 400 in chloroform-di at 400 MHz using TopSpin 3.2
spectral processing software.
[0098] The isomerization level (I) represents the relative amount
of methyl groups (--CH.sub.3) (chemical shift 0.30-1.01 ppm)
attached to the methylene backbone groups (--CH.sub.2--) (chemical
shift 1.01-1.38 ppm) and is defined by Equation (1) as shown
below,
[0099] I=m/(m+n) Equation (1) where m is NMR integral for methyl
groups with chemical shifts between 0.30.+-.0.03 to 1.01.+-.0.03
ppm, and n is NMR integral for methylene groups with chemical
shifts between 1.01.+-.0.03 to 1.38.+-.0.10 ppm.
Example A
[0100] An alkylated phenol and alkylated phenate were prepared in
substantially the same manner as in U.S. Pat. No. 8,580,717 using a
C.sub.20-24 isomerized normal alpha olefin. The isomerization level
of the alpha olefin is about 0.26. The resulting product calcium
content was 9.66%; 3.41% of sulfur, 8.2% unreacted alkylphenol and
had a kinematic viscosity at 100.degree. C. of 319 cSt. The
estimated TBN was about 400 mg KOH/g on an oil free basis. The
diluent oil was 35 wt. %.
Comparative Example A
[0101] An alkylated phenol and alkylated phenate were prepared
using a propylene tetramer available from Chevron Oronite. The
resulting product calcium content was 9.66%; 3.41% of sulfur, 8.2%
unreacted alkylphenol and had a kinematic viscosity at 100.degree.
C. of 319 cSt. The TBN was 380 mg KOH/g on an actives basis. The
diluent oil was 31.4 wt. %.
Baseline 1
[0102] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide a finished oil having a HTHS
viscosity at 150.degree. C. of 1.4 cP: [0103] (1) an ethylene
carbonate post-treated bis-succinimide; [0104] (2) a borated
bis-succinimide dispersant; [0105] (3) 0.10 wt. % in terms of
calcium content of an overbased calcium sulfonate detergent; [0106]
(4) 0.05 wt. % in terms of magnesium content, of an overbased
magnesium sulfonate detergent; [0107] (5) 770 ppm in terms of
phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0108] (6) a sulfurized molybdenum succinimide complex; [0109] (7)
a borated organic friction modifier; [0110] (8) an alkylated
diphenylamine antioxidant; [0111] (9) a foam inhibitor; [0112] (10)
2.5 wt. % of a non-dispersant polyalkylmethacrylate comb viscosity
modifier having a PSSI of 1; and [0113] (11) the remainder, a Group
II base oil (YUBASE.RTM. 2).
Example 1
[0114] To formulation baseline 1 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 1
[0115] To formulation baseline 1 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Baseline 2
[0116] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide an SAE 0W-8 finished oil: [0117]
(1) an ethylene carbonate post-treated bis-succinimide; [0118] (2)
a borated bis-succinimide dispersant; [0119] (3) 0.10 wt. % in
terms of calcium content of an overbased calcium sulfonate
detergent; [0120] (4) 0.05 wt. % in terms of magnesium content, of
an overbased magnesium sulfonate detergent; [0121] (5) 770 ppm in
terms of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0122] (6) a sulfurized molybdenum succinimide complex; [0123] (7)
a borated organic friction modifier; [0124] (8) an alkylated
diphenylamine antioxidant; [0125] (9) a foam inhibitor; [0126] (10)
3.0 wt. % of a non-dispersant polyalkylmethacrylate viscosity
modifier having a PSSI of 1; and [0127] (11) the remainder, a Group
II base oil (YUBASE.RTM. 3).
Example 2
[0128] To formulation baseline 2 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 2
[0129] To formulation baseline 2 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Baseline 3
[0130] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide an SAE 0W-12 finished oil: [0131]
(1) an ethylene carbonate post-treated bis-succinimide; [0132] (2)
a borated bis-succinimide dispersant; [0133] (3) 0.10 wt. % in
terms of calcium content of an overbased calcium sulfonate
detergent; [0134] (4) 0.05 wt. % in terms of magnesium content, of
an overbased magnesium sulfonate detergent; [0135] (5) 770 ppm in
terms of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0136] (6) a sulfurized molybdenum succinimide complex; [0137] (7)
a borated organic friction modifier; [0138] (8) an alkylated
diphenylamine antioxidant; [0139] (9) a foam inhibitor; [0140] (10)
2.0 wt. % of a non-dispersant polyalkylmethacrylate viscosity
modifier having a PSSI of 1; and [0141] (11) the remainder, a Group
III base oil (YUBASE.RTM. 4).
Example 3
[0142] To formulation baseline 3 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 3
[0143] To formulation baseline 3 was added 0.04 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Baseline 4
[0144] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide a finished oil having a HTHS
viscosity at 150.degree. C. of 1.4 cP: [0145] (1) an ethylene
carbonate post-treated bis-succinimide; [0146] (2) a borated
bis-succinimide dispersant; [0147] (3) 0.05 wt. % in terms of
magnesium content, of an overbased magnesium sulfonate detergent;
[0148] (4) 770 ppm in terms of phosphorus content, of a mixture of
a primary zinc dialkyldithiophosphate and a secondary zinc
dialkyldithiophosphate; [0149] (5) an alkylated diphenylamine
antioxidant; [0150] (6) a sulfurized molybdenum succinimide
complex; [0151] (7) a borated organic friction modifier; [0152] (8)
a foam inhibitor; [0153] (9) 2.5 wt. % of a non-dispersant
polyalkylmethacrylate comb viscosity modifier having a PSSI of 1;
and [0154] (10) the remainder, a Group II base oil (YUBASE.RTM.
2).
Example 4
[0155] To formulation baseline 4 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 4
[0156] To formulation baseline 4 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Baseline 5
[0157] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide an SAE 0W-8 finished oil: [0158]
(1) an ethylene carbonate post-treated bis-succinimide; [0159] (2)
a borated bis-succinimide dispersant; [0160] (3) 0.05 wt. % in
terms of magnesium content, of an overbased magnesium sulfonate
detergent; [0161] (4) 770 ppm in terms of phosphorus content, of a
mixture of a primary zinc dialkyldithiophosphate and a secondary
zinc dialkyldithiophosphate; [0162] (5) an alkylated diphenylamine
antioxidant; [0163] (6) a sulfurized molybdenum succinimide
complex; [0164] (7) a borated organic friction modifier; [0165] (8)
a foam inhibitor; [0166] (9) 3.0 wt. % of a non-dispersant
polyalkylmethacrylate viscosity modifier having a PSSI of 1; and
[0167] (10) the remainder, a Group II base oil (YUBASE.RTM. 3).
Example 5
[0168] To formulation baseline 5 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 5
[0169] To formulation baseline 5 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Baseline 6
[0170] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide an SAE 0W-12 finished oil: [0171]
(1) an ethylene carbonate post-treated bis-succinimide; [0172] (2)
a borated bis-succinimide dispersant; [0173] (3) 0.05 wt. % in
terms of magnesium content, of an overbased magnesium sulfonate
detergent; [0174] (4) 770 ppm in terms of phosphorus content, of a
mixture of a primary zinc dialkyldithiophosphate and a secondary
zinc dialkyldithiophosphate; [0175] (5) an alkylated diphenylamine
antioxidant; [0176] (6) a sulfurized molybdenum succinimide
complex; [0177] (7) a borated organic friction modifier; [0178] (8)
a foam inhibitor; [0179] (9) 2.0 wt. % of a non-dispersant
polyalkylmethacrylate viscosity modifier having a PSSI of 1; and
[0180] (10) the remainder, a Group III base oil (YUBASE.RTM.
4).
Example 6
[0181] To formulation baseline 6 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Example A.
Comparative Example 6
[0182] To formulation baseline 6 was added 0.14 wt. % in terms of
calcium content, of a calcium phenate detergent of Comparative
Example A.
Example B
[0183] An alkylated phenol and alkylhydroxybenzoate were prepared
in substantially the same manner as in U.S. Pat. No. 8,993,499
using a C.sub.20-24 isomerized normal alpha olefin. The
isomerization level of the alpha olefin is about 0.16. The additive
contained 6.4 wt. % Ca, and about 20 wt. % diluent oil, and had a
TBN of about 180 mgKOH/g and a basicity index of about 2.4. On an
actives basis, the TBN of this additive is about 225 mgKOH/g.
Comparative Example B
[0184] An alkylhydroxybenzoate was prepared from an alkylphenol
with an alkyl group derived from C.sub.14-18 normal alpha olefin
with at least 60 mol. % of said alkyl group having a carbon atom
number in the range of 14 to 18. The Ca wt % in the
alkylhydroxybenzoate is about 6.4 and a TBN of 297 mgKOH/g on an
actives basis. The diluent oil was 41 wt %.
Baseline 7
[0185] A lubricating oil composition was prepared that contained a
major amount of a base oil of lubricating viscosity and the
following additives, to provide an SAE 0W-8 finished oil: [0186]
(1) an ethylene carbonate post-treated bis-succinimide; [0187] (2)
a borated bis-succinimide dispersant; [0188] (4) 770 ppm in terms
of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
[0189] (5) an alkylated diphenylamine; [0190] (6) a sulfurized
molybdenum succinimide complex; [0191] (7) a borated organic
friction modifier; [0192] (8) 5 ppm in terms of silicon content, of
a foam inhibitor; [0193] (9) 0 wt. % VII and 0.4 wt. % PPD; and
[0194] (10) the remainder, a Group III base oil (YUBASE.RTM.
4).
Example 7
[0195] To formulation baseline 7 was added 0.18 wt. % in terms of
calcium content, of a calcium alkylhydroxybenzoate detergent of
Example B.
Comparative Example 7
[0196] To formulation baseline 7 was added 0.18 wt. % in terms of
calcium content, of a high overbased calcium sulfonate
detergent.
Comparative Example 8
[0197] To formulation baseline 7 was added 0.18 wt. % in terms of
calcium content, of a calcium alkylhydroxybenzoate detergent of
Comparative Example B.
ASTM D4684 Mini-Rotary Viscometer Test (MRV)
[0198] In this test, a test oil is first heated, and then cooled to
test temperature, in this case -40.degree. C., in a mini-rotary
viscometer cell. Each cell contains a calibrated rotor-stator set,
in which the rotor is rotated by means of a string wound around the
rotor shaft and attached to a weight. A series of increasing
weights are applied to the string starting with a 10 g weight until
rotation occurs to determine the yield stress. Results are reported
as Yield Stress as the applied force in Pascals. A 150 g weight is
then applied to determine the apparent viscosity of the oil. The
larger the apparent viscosity, the more likely it is that the oil
will not be continuously and adequately supplied to the oil pump
inlet. Results are reported as Viscosity in centipoise. The results
of the MRV test for each of the lubricating oil compositions are
set forth below in Table 2.
Scanning Brookfield
[0199] Scanning Brookfield Viscosity: ASTM D 5133 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 D 5133, 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 D 5133 is intended to relate to an oil's pumpability at
low temperatures. The test reports the temperature at which the
sample reaches 40,000 cP or the viscosity at -40.degree. C. 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 current API SL/ILSAC GF-5 specifications for
passenger car engine oils require a maximum gelation index of 12.
Results are shown below in Table 2.
Pour Point (JIS K 2269)
[0200] A 45 ml sample is warmed in a test tube up to 45.degree. C.
and cooled by a specified method. The test tube is taken from the
cooling bath each time the temperature of the sample drops by
2.5.degree. C., the temperature at which the sample stays
thoroughly motionless for 5 sec. is read and 2.5.degree. C. is
added to this value and the result is taken as the pour point.
TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Ex. 1 Ex. 1 Ex. 2 Ex. 2
Ex. 3 Ex. 3 Kinematic 3.789 3.791 4.707 4.707 5.676 5.681 Viscosity
(100.degree. C.), mm.sup.2/s Viscosity Index 194 195 193 193 165
165 CCS Viscosity 1010 1008 1906 1891 4361 4388 (-35.degree. C.),
cP HTHS Viscosity 1.42 1.41 1.75 1.75 2.07 2.07 (150.degree. C.),
cP MRV Yield Stress No Yield No No Yield No 210 < 140 <
(-40.degree. C.) Pa Stress Yield Stress Yield Y .ltoreq. 245 Y
.ltoreq. 175 Stress Stress Viscosity 1,826 1,842 3,513 3,577
589,253 282,118 (-40.degree. C.) mPa s Scanning Brookfield
Viscosity (mPa s 1,913 1,886 3,628 3,266 104,563 105,254 @ .degree.
C.) @ @ @ @ @ @ -39.9 -39.9 -40.0 -40.0 -33.3 -33.3 Gelation Index
3.6 3.7 5.6 5.0 12.6 14.6 (@ .degree. C.) @ @ @ @ @ @ -38.1 -38.4
-33.9 -35.9 -28.1 -29.4 Pour Point (JIS K 2269) .degree. C.
.ltoreq.-57.5 .ltoreq.-57.5 -47.5 -47.5 -22.5 -22.5 Comp. Comp.
Comp. Ex. 4 Ex. 4 Ex. 5 Ex. 5 Ex. 6 Ex. 6 Kinematic 3.834 3.841
4.780 4.790 5.749 5.759 Viscosity (100.degree. C.), mm.sup.2/s
Viscosity Index 193 193 195 196 166 166 CCS Viscosity 1046 1037
1964 1955 4544 4552 (-35.degree. C.), cP HTHS Viscosity 1.42 1.42
1.72 1.74 2.06 2.07 (150.degree. C.), cP MRV Yield Stress No Yield
No Yield No Yield No 245 < 210 < (-40.degree. C.) Pa Stress
Stress Stress Yield Y .ltoreq. 280 Y .ltoreq. 245 Stress Viscosity
1,914 1,888 4,225 3,772 609,321 555,107 (-40.degree. C.) mPa s
Scanning Brookfield Viscosity (mPa s 2,202 1,655 4,114 3,680
105,254 104,563 @.degree. C.) @ @ @ @ @ @ -40.1 -39.9 -40.1 -40.1
-36.6 -36.0 Gelation Index 5.5 No 5.5 6.8 7.0 7.5 (@.degree. C.) @
detection @ @ @ @ -38.0 -33.9 -34.0 -30.7 -29.5 Pour Point (JIS K
2269) .degree. C. -50.0 .ltoreq.-57.5 -37.5 -40.0 -15.0 -20.0
[0201] It is apparent by the data that the formulations containing
the phenate of Example A derived from isomerized normal alpha
olefin showed superior low temperature properties by one or more
measures compared to the phenate detergent that was not derived
from isomerized normal alpha olefin. The effect is greater at
higher concentrations of the detergent.
Plint TE 77 High Frequency Friction Machine
[0202] Boundary friction coefficient measurements for the Examples
and Comparative Examples were obtained using a Plint TE-77 High
Frequency Friction Machine (commercially available from Phoenix
Tribology).
[0203] A 5 mL sample of test oil was placed in the apparatus for
each test. The TE-77 was run at 100.degree. C. and 56N of load was
placed on the testing specimen. The reciprocating speed was swept
from 10 Hz to 1 Hz, and coefficient of friction data was collected
throughout the test. The friction coefficient measurements are
shown in Table 3.
TABLE-US-00003 TABLE 3 Comp. Ex. 7 Comp Ex. 8 Ex. 7 Kinematic
Viscosity (100.degree. C.), 5.14 5.33 5.40 mm.sup.2/s Viscosity
Index 135.0 136.4 136.4 CCS Viscosity (-35.degree. C.), cP 4230
4381 4881 HTHS Viscosity (150.degree. C.), cP 1.89 1.93 1.93 Plint
TE77 Coefficient of Friction 1 Hz 0.133 0.092 0.077 (100.degree.
C.) 2 Hz 0.132 0.103 0.091 3 Hz 0.125 0.103 0.096 4 Hz 0.120 0.102
0.097 5 Hz 0.112 0.099 0.099 6 Hz 0.107 0.096 0.098 7 Hz 0.102
0.092 0.098 8 Hz 0.097 0.087 0.096 9 Hz 0.092 0.082 0.093 10 Hz
0.089 0.078 0.091
[0204] Coefficient of friction data collected for these oils at
reciprocating speeds of 1 to 2 Hz are in a boundary friction
regime.
[0205] The boundary friction regime is an important consideration
in the design of low viscosity engine oils. Boundary friction
occurs when the fluid film separating two surfaces becomes thinner
than the height of asperities on the surfaces. The resulting
surface to surface contact creates undesirable high friction and
poor fuel economy in an engine. Boundary friction in an engine can
occur under high loads, low engine speeds and at low oil
viscosities. Low viscosity engine oils make the engine more
susceptible to operating in boundary friction conditions due to the
oil's thinner, less robust film. Because additives--not base
oil--influence the coefficient of friction under boundary
conditions, additives that demonstrate lower coefficients of
friction under boundary conditions in the TE-77 will give superior
fuel economy in a low viscosity oil in an engine.
[0206] Based on the boundary friction regime results from Example
7, it is evident that the formulation containing the
alkylhydroxybenzoate derived from isomerized normal alpha olefin is
superior to those not derived from isomerized normal alpha
olefin.
* * * * *