Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICATING OIL COMPOSITIONS CONTAINING DETERGENT COMPOUNDS
This application claims the benefit of and priority to U.S. Provisional
Application Ser. No.
62/527,089, filed June 30, 2017.
BACKGROUND OF THE DISCLOSURE
[0001] Overbased detergents are well described to provide lubricating
properties.
Often such detergent additives are proportioned with other lubricating
additives to provide
lubricating oil compositions that exhibit certain desired lubricating
properties. Metal-
containing detergents function both as detergents to control deposits, and as
acid neutralizers
or rust inhibitors, thereby reducing wear, controlling corrosion, and
extending engine life.
[0002] The present disclosure generally relates to lubricating oil
compositions which
simultaneously achieve wear control and corrosion inhibition, while also
achieving improved
fuel economy. The lubricating oil compositions are suitable for automotive
engines,
motorcycle engines, natural gas engines, dual fuel engines, railroad
locomotive engines,
mobile natural gas engines, and as functional fluids for automotive and
industrial
applications.
[0003] Among other factors, the present invention is based on the
surprising
discovery that a lubricating oil composition containing more highly overbased
metal
hydroxybenzoate detergent, having a TBN of 600 mgK01-1/g or greater on an
actives basis,
exhibits improved lubricating properties such as superior performance at low
temperatures,
BN retention, oxidative and thermal stability, corrosion resistance, and
oxidative and thermal
stability, in addition to providing a more cost effective formulating approach
over the use of
overbased hydroxybenzoate detergent technology previously described in the
art.
SUMMARY OF THE DISCLOSURE
[0004] In accordance with one embodiment of the present disclosure, there
is
provided a lubricating oil composition which comprises:
(a) a major amount of an oil of lubricating viscosity, and
(b) one or more detergents comprising at least one alkylhydroxybenzoate
compound derived from isomerized NAO having from about 10 to about 40
carbon atoms,
1
wherein the TBN of the alkylhydroxybenzoate compound is at least 600
mgKOH/gm on an actives basis.
100051 Also provided is a method of lubricating an engine comprising
lubricating said
engine with a lubricating oil composition comprising:
(a) a major amount of an oil of lubricating viscosity,
(b) one or more detergents comprising at least one alkylhydroxybenzoate
compound derived from isomerized NAO having from about 10 to 40 carbon
atoms,
wherein the TBN of the alkylhydroxybenzoate compound is at least 600
mgKOH/gm on an actives basis.
[0005a1 In accordance with another, there is a lubricating oil composition
comprising:
(a) an oil of lubricating viscosity in excess of 50 weight % of the
lubricating oil
composition, and
(b) one or more detergents comprising at least one alkylhydroxybenzoate
compound derived from isomerized normal alpha olefin (NAO) having from 10
to 40 carbon atoms,
wherein the TBN of the alkylhydroxybenzoate compound determined in
accordance with ASTM D2896 is at least 600 mgKOH/gm on an actives basis;
wherein the alkylhydroxybenzoate compound is a Ca alkylhydroxybenzoate
compound; and
the lubricating oil composition comprises 0.01 to 2 wt.% in terms of Ca
content
of the alkylhydroxybenzoate compound.
DETAILED DESCRIPTION OF THE DISLCOSURE
[0006] While the invention is susceptible to various modifications and
alternative
forms, specific embodiments thereof are herein described in detail. It should
be understood,
however, that the description herein of specific embodiments is not intended
to limit the
invention to the particular forms disclosed, but on the contrary, the
intention is to cover all
modifications, equivalents, and alternatives falling within the spirit and
scope of the invention
as defined by the appended claims.
00071 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.
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DEFINITIONS
[0008] As used herein, the following terms have the following meanings,
unless
expressly stated to the contrary. In this specification, the following words
and expressions, if
and when used, have the meanings given below.
[0009] A "major amount" means in excess of 50 weight % of a composition.
[0010] 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.
[0011] "Active ingredients" or "actives" or "oil free" refers to additive
material that is
not diluent or solvent.
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[0012] All percentages reported are weight % on an active ingredient basis
(i.e., without
regard to carrier or diluent oil) unless otherwise stated.
[0013] The abbreviation "ppm" means parts per million by weight, based on
the total
weight of the lubricating oil composition.
[0014] Total base number (1'13N) was determined in accordance with ASTM
D2896.
[0015] Metal ¨ The term "metal" refers to alkali metals, alkaline earth
metals, or
mixtures thereof.
[0016] High temperature high shear (HTHS) viscosity at 150 C was
determined in
accordance with ASTM D4863.
[0017] Kinematic viscosity at 100 C (KV100) was determined in accordance
with
ASTM D445.
[0018] Cold Cranking Simulator (CCS) viscosity at -35 C was determined in
accordance with ASTM D5293.
[0019] 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.
[0020] 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 beginning and end of the chain.
[0021] 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.
[0022] All ASTM standards referred to herein are the most current versions
as of the
filing date of the present application.
[0023] In one aspect, the present disclosure is directed to a lubricating
oil composition
comprising:
3
(a) a major amount of an oil of lubricating viscosity, and
(b) one or more detergents comprising at least one alkylhydroxybenzoate
compound derived from isomerized normal alpha olefins having from about 10
to 40 carbon atoms,
wherein the TBN of the alkylhydroxybenzoate compound is at least 600
mgKOH/gm on an actives basis.
100241 In another aspect, provided is a method of lubricating an engine
comprising
lubricating said engine with a lubricating oil composition comprising:
(a) a major amount of an oil of lubricating viscosity, and
(b) one or more detergents comprising at least one alkylhydroxybenzoate
compound derived from isomerized noimal alpha olefins having from about
to 40 carbon atoms,
wherein the TBN of the alkylhydroxybenzoate compound is at least 600
mgKOH/gm on an actives basis.
100251 Alkylhydroxybenzoate Detergent compound derived from C10 - C40
isomerized Normal Alpha Olefin (NAO)
100261 In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
compound derived from CID - Cao isomerized NAO has a TBN of at least 600, 600
or greater,
from 600 - 800, 600 - 750, 600 - 700 mgKOH/gram on an actives basis.
100271 In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from Cio - C40 isomerized NAO with a TBN of 600 mgKOH/gram or greater
on an oil-
free basis can be prepared as described in US Patent 8,993,499.
100281 In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from Cio - Cao isomerized NAO is a Ca alkylhydroxybenzoate detergent.
[0029] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from Cio - C40 isomerized NAO can be an alkylated hydroxybenzoate
detergent. In one
embodiment, the detergent can be a salicylate detergent. In another
embodiment, the detergent
can be a carboxylate detergent. In one aspect of the present disclosure, the
alkylhydroxybenzoate detergent with a TBN of 600 mgKOH/gram or greater on an
oil-free
basis is made from an alkylphenol having an alkyl group derived from an
isomerized alpha
olefin having from about 14 to about 28, or from about 20 to about 24 carbon
atoms per
molecule.
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[0030] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from Cio - Cao isomerized NAO with a TBN of 600 mgKOH/gram or greater
on an
actives basis is made from one or more alkylphenols with an alkyl group
derived from Cm -
C40 isomerized NAO and one or more alkylphenols with an alkyl group different
from C10 -
C40 isomerized NAO. Preferably the one or more alkylphenols with an alkyl
group different
from Cm - C40 isomerized NAO has a highly branched alkyl group of at least 9
carbon atoms,
from 9 to 24, and from 10-15 carbon atoms. In one aspect of the present
disclosure, the
lubricating oil composition comprises about 0.01 to 2 wt.% in terms of Ca
content of the
alkylhydroxybenzoate detergent derived from Cio - Cao isomerized NAO with a
TBN of 600
mgKOH/gram or greater on an actives basis, preferably 0.1 to 1 wt. %, more
preferably 0.05
to 0.5 wt. %, more preferably 0.1 to 0.5 wt%. In one aspect of the present
disclosure, the
lubricating oil composition comprises the alkylhydroxybenzoate derived from
Cio - C40
isomerized NAO with 113N 600 or more on an active basis is an automotive
engine oil, a gas
engine oil, a motorcycle oil, a dual fuel engine oil, a mobile gas engine oil,
or a locomotive
engine oil.
[0031] In one aspect of the present disclosure, the lubricating oil
composition
comprises the alkylhydroxybenzoate derived from Cm - Ca() isomerized NAO with
a TBN of
600 mgKOH/gram or more on an oil-free basis is a functional fluid for
automotive and
industrial applications, such as transmission oil, hydraulic oil, tractor
fluid, gear oil, et. In one
aspect of the present disclosure, the lubricating oil composition comprises
the
alkylhydroxybenzoate derived from Cm - Cao isomerized NAO with a TBN of 600
mgKOH/gram or more on an actives basis is a multi-grade oil.
[0032] In one aspect of the present disclosure, the lubricating oil
composition
comprises the alkylhydroxybenzoate derived from Cm - C40 isomerized NAO with a
'TBN of
600 mgKOH/gram or more on an actives basis lubricates crankcase, gear as well
as clutches.
Additional Detergents
[0033] The lubricating oil composition of the present invention can further
contain one or
more ovcrbased detergents having a IBN of 10-800, 10-700, 30-690, 100-600, 150-
600, 150-
500, 200-450 mg KOH/g on an actives basis.
[0034] Detergents that may be used include oil-soluble overbased
sulfonate, non-
sulfur containing phenate, sulfurized phenates, salixarate, salicylate,
saligenin, complex
detergents and naphthenate detergents and other oil-soluble
alkylhydroxybenzoates of a
metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium,
potassium,
lithium, calcium, and magnesium. The most commonly used metals are calcium and
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magnesium, which may both be present in detergents used in a lubricant, and
mixtures of
calcium and/or magnesium with sodium.
100351 Overbased metal detergents are generally produced by carbonating a
mixture
of hydrocarbons, detergent acid, for example: sulfonic acid,
alkylhydroxybenzoate etc., metal
oxide or hydroxides (for example calcium oxide or calcium hydroxide) and
promoters such as
xylene, methanol and water. For example, for preparing an overbased calcium
sulfonate, in
carbonation, the calcium oxide or hydroxide reacts with the gaseous carbon
dioxide to form
calcium carbonate. The sulfonic acid is neutralized with an excess of CaO or
Ca(OH)2, to
form the sulfonate.
100361 Overbased detergents may be low overbased, e.g., an overbased salt
having a
IBN below 100 on an actives basis. In one embodiment, the TBN of a low
overbased salt
may be from about 30 to about 100. In another embodiment, the TBN of a low
overbased salt
may be from about 30 to about 80. Overbased detergents may be medium
overbased, e.g., an
overbased salt having a TBN from about 100 to about 250. In one embodiment,
the 1BN of a
medium overbased salt may be from about 100 to about 200. In another
embodiment, the
I'BN of a medium overbased salt may be from about 125 to about 175. Overbased
detergents
may be high overbased, e.g., an overbased salt having a TBN above 250. In one
embodiment, the 113N of a high overbased salt may be from about 250 to about
800 on an
actives basis.
100371 In one embodiment, the detergent can be one or more alkali or
alkaline earth
metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid. Suitable
hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy
aromatic
hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups. Suitable
hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinonc,
pyrogallol,
cresol, and the like. The preferred hydroxyaromatic compound is phenol.
100381 The alkyl substituted moiety of the alkali or alkaline earth metal
salt of an
alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha
olefin having
from about 10 to about 80 carbon atoms. The olefins employed may be linear,
isomerized
linear, branched or partially branched linear. The olefin may be a mixture of
linear olefins, a
mixture of isomerized linear olefins, a mixture of branched olefins, a mixture
of partially
branched linear or a mixture of any of the foregoing.
100391 In one embodiment, the mixture of linear olefins that may be used
is a mixture
of normal alpha olefins selected from olefins having from about 10 to about 40
carbon atoms
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per molecule. In one embodiment, the normal alpha olefins are isomerized using
at least one
of a solid or liquid catalyst.
[0040] In one embodiment, at least about 50 mole%, at least about 75
mole%, at least
about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least
about 95 mole%
of the alkyl groups contained within the alkali or alkaline earth metal salt
of an alkyl-
substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an
alkaline earth
metal salt of an alkyl-substituted hydroxybenzoic acid detergent are a C20 or
higher. In
another embodiment, the alkali or alkaline earth metal salt of an alkyl-
substituted
hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of
an alkyl-
substituted hydroxybenzoic acid that is derived from an alkyl-substituted
hydroxybenzoic
acid in which the alkyl groups are C20 to about C28 normal alpha-olefins. In
another
embodiment, the alkyl group is derived from at least two alkylated phenols.
The alkyl group
on at least one of the at least two alkyl phenols is derived from an
isomerized alpha olefin.
The alkyl group on the second alkyl phenol may be derived from branched or
partially
branched olefins, highly isornerized olefins or mixtures thereof,
[0041] In another embodiment, the alkali or alkaline earth metal salt of
an alkyl-
substituted hydroxyaromatic carboxylic acid is a salicylate derived from an
alkyl group with
20-40 carbon atoms, preferably 20-28 carbon atoms, more preferably, isomerized
20-24
NAO.
[0042] Sulfonates may be prepared from sulfonic acids which are typically
obtained
by the sulfonation of alkyl substituted aromatic hydrocarbons such as those
obtained from the
fractionation of petroleum or by the alkylation of aromatic hydrocarbons.
Examples included
those obtained by alkylating benzene, toluene, xylenc, naphthalene, diphenyl
or their halogen
derivatives. The alkylation may be carried out in the presence of a catalyst
with alkylating
agents having from about 3 to more than 70 carbon atoms. The alkaryl
sulfonates usually
contain from about 9 to about 80 or more carbon atoms, preferably from about
16 to about 60
carbon atoms, preferably about 16 to 30 carbon atoms, and more preferably 20-
24 carbon
atoms per alkyl substituted aromatic moiety.
[0043] Metal salts of phenols and sulfurized phenols, which are
sulfiirized phenate
detergents, are prepared by reaction with an appropriate metal compound such
as an oxide or
hydroxide and neutral or overbased products may be obtained by methods well
known in the
art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a
sulfur
containing compound such as hydrogen sulfide, sulfur monohalide or sulfur
dihalide, to form
7
products which are generally mixtures of compounds in which 2 or more phenols
are bridged
by sulfur containing bridges.
[0044] Additional details regarding the general preparation of sulfurized
phenates can
be found in, for example, U.S. Pat. Nos. 2,680,096; 3,178,368, 3,801,507, and
8,580,717.
[0045] Considering now in detail, the reactants and reagents used in the
present
process, first all allotropic forms of sulfur can be used. The sulfur can be
employed either as
molten sulfur or as a solid (e.g., powder or particulate) or as a solid
suspension in a
compatible hydrocarbon liquid.
[0046] It is desirable to use calcium hydroxide as the calcium base because
of its
handling convenience versus, for example, calcium oxide, and also because it
affords
excellent results. Other calcium bases can also be used, for example, calcium
alkoxides.
[0047] Suitable alkylphenols which can be used are those wherein the alkyl
substituents contain a sufficient number of carbon atoms to render the
resulting overbased
sulfurized calcium alkylphenate composition oil-soluble. Oil solubility may be
provided by a
single long chain alkyl substitute or by a combination of alkyl substituents.
Typically, the
alkylphenol used will be a mixture of different alkylphenols, e.g., C20 to C24
alkylphenol.
100481 In one embodiment, suitable alkyl phenolic compounds will be derived
from
isomerized alpha olefin alkyl groups having from about 10 to about 40 carbon
atoms per
molecule, having an isomerized level (1) of the alpha olefin between from
about 0.1 to about
0.4. In one embodiment, suitable alkyl phenolic compounds will be derived from
alkyl groups
which are branched olefinic propylene oligomers or mixture thereof having from
about 9 to
about 80 carbon atoms. In one embodiment, the branched olefinic propylene
oligomer or
mixtures thereof have from about 9 to about 40 carbon atoms. In one
embodiment, the
branched olefinic propylene oligomer or mixtures thereof have from about 9 to
about 18
carbon atoms. In one embodiment, the branched olefinic propylene oligomer or
mixtures
thereof have from about 9 to about 12 carbon atoms.
100491 In one embodiment, suitable alkyl phenolic compounds comprise
distilled
cashew nut shell liquid (CNSL) or hydrogenated distilled cashew nut shell
liquid. Distilled
CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols, where
the
hydrocarbyl group is linear and unsaturated, including cardanol. Catalytic
hydrogenation of
distilled CNSL gives rise to a mixture of meta-hydrocarbyl substituted phenols
predominantly rich in 3-pentadecylphenol.
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[0050] The alkylphenols can be para-alkylphenols, meta-alkylphenols or
ortho
alkylphenols. Since it is believed that p-alkylphenols facilitate the
preparation of highly
overbased calcium sulfurized alkylphenate where overbased products are
desired, the
alkylphenol is preferably predominantly a para alkylphenol with no more than
about 45 mole
percent of the alkylphenol being ortho alkylphenols; and more preferably no
more than about
35 mole percent of the alkylphenol is ortho alkylphenol. Alkyl-hydroxy
toluenes or xylenes,
and other alkyl phenols having one or more alkyl substituents in addition to
at least one long
chained alkyl sub stituent can also be used. In the case of distilled cashew
nut shell liquid,
the catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta-
hydroearbyl
substituted phenols.
[0051] In one embodiment, the one or more overbased detergent can be a
complex or
hybrid detergent which is known in the art as comprising a surfactant system
derived from at
least two surfactants described above.
[0052] In one embodiment, the one or more overbased detergent can be a
salicylate
with an alkyl group having 20-28 carbon atoms, more preferably 20-24Cearbon
atoms. In
another embodiment, the one or more overbased detergent can be a salicylate
with an alkyl
group derived from Cm-18NA and contribute less than 0.05 wt%, preferably less
than 0.025
wt%, more preferably less than 0.01 wt% in terms of Ca content to the
lubricating oil.
[0053] Generally, the amount of the detergent can be from about 0.001 wt.
% to about
50 wt. %, or from about 0.05 wt. % to about 25 wt. %, or from about 0.1 wt. %
to about 20 wt.
%, or from about 0.01 to 15 wt. % based on the total weight of the lubricating
oil composition.
Antiwear Agents
[0054] The lubricating oil composition disclosed herein can comprise one
or more
antiwear agent. Antiwear agents reduce wear of metal parts. Suitable anti-wear
agents include
dihydrocarbyl dithiophosphatc metal salts such as zinc dihydrocarbyl
dithiophosphates
(ZDDP) of formula (Formula 1):
Zn[S¨P(=S)(0R1)(0R2)12 Formula 1,
wherein and R2 may be the same of different hydrocarbyl radicals having from 1
to
18 (e.g., 2 to 12) carbon atoms and including radicals such as alkyl, alkenyl,
aryl, arylalkyl,
alkaryl and cycloaliphatic radicals. Particularly preferred as It' and R2
groups are alkyl groups
having from 2 to 8 carbon atoms (e.g., the alkyl radicals may be ethyl, n-
propyl, isopropyl, n-
butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-
ethylhexyl). In order to
obtain oil solubility, the total number of carbon atoms (i.e., R4R2) will be
at least 5. The zinc
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dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl
dithiophosphates. The zinc
dialkyl dithiophosphate is a primary, secondary zinc dialkyl dithiophosphate,
or a combination
thereofZDDP may be present at 3 wt. % or less (e.g., 0.1 to 1.5 wt. %, or 0.5
to 1.0 wt %) of
the lubricating oil compositionin one embodiment, the lubricating oil
composition containing
the magnesium salicylate detergent described herein further comprises an
antioxidant
compound. In one embodiment, the antioxidant is a diphenylamine antioxidant.
In another
embodiment, the antioxidant is a hindered phenol antioxidant. In yet another
embodiment, the
antioxidant is a combination of a diphenylamine antioxidant and a hindered
phenol antioxidant.
Antioxidants
[0055] The
lubricating oil composition disclosed herein can comprise one or more
antioxidant. Antioxidants reduce the tendency of mineral oils during to
deteriorate during
service. Oxidative deterioration can be evidenced by sludge in the lubricant,
varnish-like
deposits on the metal surfaces, and by viscosity growth. Suitable antioxidants
include hindered
phenols, aromatic amines, and sulfurized alkylphenols and alkali and alkaline
earth metals salts
thereof.
[0056] The
hindered phenol antioxidant often contains a secondary butyl and/or a
tertiary butyl group as a sterically hindering group. The phenol group may be
further substituted
with a hydrocarbyl group (typically linear or branched alkyl) and/or a
bridging group linking
to a second aromatic group. Examples of suitable hindered phenol antioxidants
include 2,6-di-
tert-butylphenol; 4-methyl-2,6-di-tert-butylphenol; 4-ethyl-2,6-di-tert-
butylphenol; 4-propy1-
2,6-di-tert-butylphenol; 4-butyl-2,6-di-tert-
butylphenol; and 4-dodecy1-2,6-di-tert-
butylphenol. Other useful hindered phenol antioxidants include 2,6-di-alkyl-
phenolic propionic
ester derivatives such as IRGANOV9 L-135 from Ciba and bis-phenolic
antioxidants such as
4,4 ' -bi s(2,6-di-te rt-butylphenol) and 4,4 '-methylenebis(2,6-di-tert-
butylphenol).
Typical aromatic amine antioxidants have at least two aromatic groups attached
directly to one
amine nitrogen. Typical aromatic amine antioxidants have alkyl substituent
groups of at least
6 carbon atoms. Particular examples of aromatic amine antioxidants useful
herein include 4,4'-
dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-l-naphthylamine, N-
(4-tert-
octypheny1)-1-naphthylamine, and N-(4-octylpheny1)-1-
naphthylamine.Antioxidants may be
present at 0.01 to 5 wt. % (e.g., 0.1 to 2 wt. %) of the lubricating oil
composition.
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Dispersants
[0057] The lubricating oil composition disclosed herein can comprise one
or more
dispersant. Dispersants maintain in suspension materials resulting from
oxidation during
engine operation that are insoluble in oil, thus preventing sludge
flocculation and precipitation
or deposition on metal parts. Dispersants useful herein include nitrogen-
containing, ashless
(metal-free) dispersants known to effective to reduce formation of deposits
upon use in gasoline
and diesel engines.
100581 Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl
succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid,
hydroxyesters of
hydrocarbyl-substituted succinic acid, and Mannich condensation products of
hydrocarbyl-
substituted phenols, formaldehyde and polyamines. Also suitable are
condensation products of
polyamines and hydrocarbyl-substituted phenyl acids. Mixtures of these
dispersants can also
be used.Basic nitrogen-containing ashless dispersants are well-known
lubricating oil additives
and methods for their preparation are extensively described in the patent
literature. Preferred
dispersants are the alkenyl succinimides and succinamides where the alkenyl-
substituent is a
long-chain of preferably greater than 40 carbon atoms. These materials are
readily made by
reacting a hydrocarbyl-substituted dicarboxylic acid material with a molecule
containing amine
functionality. Examples of suitable amines are polyamines such as polyalkylene
polyamines,
hydroxy-substituted polyamines and polyoxyalkylene polyamines.
100591 Particularly preferred ashless dispersants are the polyisobutenyl
succinimides
formed from polyisobutenyl succinic anhydride and a polyalkylene polyamine
such as a
polyethylene polyamine of formula 2:
NH2(CH2CH2NH)zH Formula 2,
wherein z is 1 to 11. The polyisobutenyl group is derived from polyisobutene
and preferably
has a number average molecular weight (Mn) in a range of 700 to 3000 Daltons
(e.g., 900 to
2500 Daltons). For example, the polyisobutenyl succinimide may be a bis-
succinimide derived
from a polyisobutenyl group having a Mn of 900 to 2500 Daltons. As is known in
the art, the
dispersants may be post-treated (e.g., with a boronating agent or a cyclic
carbonate, ethylene
carbonate etc).
[0060] Nitrogen-containing ashless (metal-free) dispersants are basic, and
contribute to
the TBN of a lubricating oil composition to which they are added, without
introducing
additional sulfated ash.Dispersants may be present at 0.1 to 10 wt. % (e.g., 2
to 5 wt. %) of the
lubricating oil composition.
11
Foam Inhibitors
[0061] The lubricating oil composition disclosed herein can comprise one or
more
foam inhibitor that can break up foams in oils. Non-limiting examples of
suitable foam
inhibitors or anti-foam inhibitors include silicone oils or
polydimethylsiloxanes,
fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene
glycols), branched
polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers,
polyalkoxyamines and
combinations thereof.
Additional Co-Additives
[0062] 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 Monier 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). 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.
100631 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.
[0064] 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.
[0065] 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
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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.
[0066] 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.
Oil of lubricatine viscosity
[0067] 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.
[0068] 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.
[0069] Synthetic lubricating oils include hydrocarbon oils such as
polymerized and
interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-
isobutylene
copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes),
poly(1-decene s);
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.
[0070] 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
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glycol, diethylene glycol monoether, propylene glycol). Specific examples of
these esters
include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fiimarate,
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.
[0071] Esters useful as synthetic oils also include those made from C5 to
C12
monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol,
trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
[0072] The base oil may be derived from Fischer-Tropsch synthesized
hydrocarbons.
Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas
containing H2 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.
[0073] 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 the 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.
[0074] 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.
[0075] 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:
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Table 1
Base Oil Properties
Groue Saturates(, wt. % Sulfur(o, wt. % Viscosity Index40
Group I <90 and/or >0.03 80 to <120
Group II >90 <0.03 80 to <120
Group III 290 <0.03 >120
Group IV Polyalphaolefins (PA0s)
Group V All other base stocks not included in Groups I, II, III or
IV
(a) Groups I-III are mineral oil base stocks.
(b) Determined in accordance with ASTM D2007.
(C) Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM
D4927.
Determined in accordance with ASTM D2270.
[0076] 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.
[0077] The oil of lubricating viscosity for use in the lubricating oil
compositions of this
disclosure, also referred to as a base oil, is typically present in a major
amount, e.g., an amount
of greater than 50 wt. %, preferably greater than about 70 wt. %, more
preferably from about
80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %,
based on the total
weight of the composition. The expression "base oil" as used herein shall be
understood to
mean a base stock or blend of base stocks which is a lubricant component that
is produced by
a single manufacturer to the same specifications (independent of feed source
or manufacturer's
location); that meets the same manufacturer's specification; and that is
identified by a unique
fonnula, product identification number, or both. The base oil for use herein
can be any presently
known or later-discovered oil of lubricating viscosity used in formulating
lubricating oil
compositions for any and all such applications, e.g., engine oils, marine
cylinder oils, functional
fluids such as hydraulic oils, gear oils, transmission fluids, etc.
Additionally, the base oils for
use herein can optionally contain viscosity index improvers, e.g., polymeric
alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer
or a styrene-
butadiene copolymer; and the like and mixtures thereof.
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[0078] As one
skilled in the art would readily appreciate, the viscosity of the base oil
is dependent upon the application. Accordingly, the viscosity of a base oil
for use herein will
ordinarily range from about 2 to about 2000 centistokes (cSt) at 100
Centigrade (C.).
Generally, individually the base oils used as engine oils will have a
kinematic viscosity range
at 100 C. of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16
cSt, and most
preferably about 4 cSt to about 12 cSt and will be selected or blended
depending on the desired
end use and the additives in the finished oil to give the desired grade of
engine oil, e.g., a
lubricating oil composition having an SAE Viscosity Grade of OW, 0W-8, OW-12,
OW-16, OW-
20, OW-26, OW-30, OW-40, 0W-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60,
10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and
the
like.
Lubricating Oil Compositions
[0079] 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.
[0080] 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. (Yo. 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
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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.
%.
[0081] 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. `)/0 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. (Yo as determined by ASTM D 874.
[0082] The following examples are presented to exemplify embodiments of
the
invention but are not intended to limit the invention 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 invention.
Specific details
described in each example should not be construed as necessary features of the
invention.
17
EXAMPLES
The following examples are intended for illustrative purposes only and do not
limit in any way
the scope of the present disclosure.
Isomerization level (I) and NMR method
[0083] The isomerization level (I) of the olefin was determined by hydrogen-
1 (1H)
NMR. The NMR spectra were obtained on a BrukerTM Ultrashield Plus 400 in
chloroform-d1
at 400 MHz using TopSpinTm 3.2 spectral processing software.
[0084] The isomerization level (I) represents the relative amount of methyl
groups (-
CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone groups (-
CH2-)
(chemical shift 1.01-1.38 ppm) and is defined by Equation (1) as shown below,
I = m/(m+n) Equation (I)
where m is NMR integral for methyl groups with chemical shifts between 0.3
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.
[0085] The isomerized level (I) of the alpha olefin is between from about
0.1 to about
0.4, preferably from about 0.1 to about 0.3, more preferably from about 0.12
to about 0.3.
[0086] In one embodiment, the isomerization level of the NAO is about 0.16,
and
having from about 20 to about 24 carbon atoms.
[0087] In another embodiment, the isomerization level of the NAO is about
0.26, and
having from about 20 to about 24 carbon atoms.
Baseline Formulation 1
[0088] A 5W-40 lubricating oil composition was prepared that contained a
major
amount of a base oil of lubricating viscosity and the following additives:
(1) an ethylene carbonate post-treated bis-succinimide;
(2) a zinc dialkyldithiophosphate;
(3) a mixture of antioxidants;
(4) a foam inhibitor.
Example A
[0089] An alkylated phenol and a Ca alkylhydroxybenzoate were prepared in
substantially the same manner as in U.S. Patent No. 8,993,499 using a C20_24
isomerized
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normal alpha olefin. The isomerization level of the alpha olefin is about
0.16. The resulting
alkylhydroxybenzoate composition has a 1BN of about 630 and Ca content of
about 22.4
wt.% on an oil-free basis.
Example B
[0090] An alkylated phenol and Ca alkylhydroxybenzoate were prepared in
substantially the same manner as in U.S. Patent No. 8,993,499 using a C2o-24
isomerized
normal alpha olefin. The isomerization level of the alpha olefui is about
0.16. The resulting
alkylhydroxybenzoate composition has a 113N of about 225 and Ca content of
about 8 wt.%
on an oil-free basis.
Comparative Example A
[0091] An alkylhydroxybenzoate was prepared from an alkylphenol with an
alkyl
group derived from C14-18 NAO and a TBN about 300 and Ca content about 10.6
wt. % on an
oil-free basis.
Comparative Example B
[0092] An alkylated phenol and alkylhydroxybenzoate were prepared in
substantially
the same manner as in U.S. Patent No. 8,030,258 using a C2o-28NAO available
from CP
Chem. The resulting alkylhydroxybenzoate composition has a 1BN of about 520
and Ca
content of about 18.7 wt.% on an oil-free basis.
Example 1
[0093] To baseline formulation 1 was added 0.13 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Example A and 0.05 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Example B.
Example 2
[0094] To baseline formulation 1 was added 0.13 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Example A and 0.02 wt.% in terms of Ca
content of a
sulfurized overbased Ca phenate detergent.
Example 3
[0095] To baseline formulation I was added (9.83 mmol Soap) of a Ca
alkylhydroxybenzoate detergent of Example A.
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Comparative Example 1
[0096] To baseline formulation I was added 0.13 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Comparative Example B and 0.02 wt.% in terms
of Ca
content of a sulfurized overbased Ca phenate detergent.
Comparative Example 2
[0097] To baseline formulation 1 was added (9.83 mmol of Soap) of Ca
alkylhydroxybenzoate detergent of Comparative Example B.
HTCBT Test
[0098] The ASTM D6594 HTCBT test is used to test diesel engine lubricants
to
determine their tendency to corrode various metals, specifically alloys of
lead and copper
commonly used in cam followers and bearings. Four metal specimens of copper,
lead, tin and
phosphor bronze are immersed in a measured amount of engine oil. The oil, at
an elevated
temperature (170 C), is blown with air (5 1/h) for a period of time (168 h).
When the test is
completed, the copper specimen and the stressed oil are examined to detect
corrosion and
corrosion products, respectively. The concentrations of copper, lead, and tin
in the new oil
and stressed oil and the respective changes in metal concentrations are
reported. To be a pass
the concentration of lead should not exceed 120 ppm and the copper 20 ppm.
Table 2- HTCBT
Change in Example Example Comparative
Concentration 1 2 Ex 1
(mg/kg)
Copper 5 4 4
Lead 106 123 124
Table 3¨ HTCBT (equal soap comparison)
Change in Example Comparative
Concentration 3 Ex. 2
(mg/kg)
Copper 3 2
Lead 24 44
Baseline Formulation 2
[0099] A heavy duty automotive 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 15W-40 finished oil:
(1) an ethylene carbonate post-treated bis-succinimide dispersant;
(2) 990 ppm in terms of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
(3) Moly succinimide complex providing 50 ppm of molybdenum
(4) an alkylated diphenylamine antioxidant;
(5) 5 ppm in terms of silicon content, of a foam inhibitor;
(6) 9.5 wt. % VII (additive) of Non-dispersant OCP and 0.3 wt. % PPD; and
(7) the remainder, a Group II base oil (ChevronTM 220R).
Example 4
[00100] To formulation baseline 2 was added 0.2290 wt.% in terms of calcium
content,
of a calcium alkylhydroxybenzoate detergent of Example A and 0.078 wt.% in
terms of
magnesium content a C20-C24 magnesium alkylhydroxybenzoate detergent, made
from
isomerized NAO with isomerization level of 0.16. Properties: TBN (mgKOH/g) =
199 in 35
wt% of diluent oil.
Comparative Example 3
[00101] To formulation baseline 2 was added 0.2290 wt.% in terms of calcium
content,
of a calcium alkylhydroxybenzoate detergent of Example A and 0.075 wt.% in
terms of
magnesium content a C14-C18 magnesium alkylhydroxybenzoate detergent, made
from alpha
olefin. Properties: TBN (mgKOH/g) = 236; Mg (wt.%) = 5.34.
Oxidator Bx test
[00102] A 25 g sample was weighted into a special glass oxidator cell. A
catalyst was
added, followed by inserting a glass stirrer. The cell was then sealed and
placed in an oil bath
maintained at 340 F and connected to the oxygen supply. One liter of oxygen
was fed into
the cell while the stirrer agitated the oil sample. The test was run until 1
liter of oxygen was
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consumed by the sample and the total time, in hours, of the sample run was
reported. Higher
hours to 1 Liter means better oxidation performance. Results are given in
Table 4 below.
Table 4
Ex. 4 Comp.
Ex. 3
Hours to
39.3 36.9
1 Ltr.
Example C
[00103] An alkylated phenol and a Ca alkylhydroxybenzoate were prepared in
substantially the same manner as in U.S. Patent No. 8,993,499 using a C20-24
isomerized
normal alpha olefin. The isomeriz.ation level of the alpha olefin is about
0.16. The resulting
alkythydroxybenzoate composition has a TBN of about 120 and Ca content of
about 4.2 wt.%
on an oil-free basis.
Baseline Formulation 3
[00104] A passenger car automotive 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 5W-30 finished oil:
(1) an ethylene carbonate post-treated bis-succinimide dispersant and borated
dispersant;
(2) 770 ppm in terms of phosphorus content, of a mixture of a primary zinc
dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate;
(3) Moly succinimide complex providing 180 ppm of molybdenum
(4) an alkylated diphenylamine antioxidant;
(5) a borated friction modifier;
(5) 5 ppm in terms of silicon content, of a foam inhibitor;
(6) 9.5 wt. % VII (additive) of Non-dispersant OCP and 0.3 wt. % PPD; and
(7) the remainder, a Group III base oil.
Example 5
[00105] To formulation baseline 3 was added a mixture of both a calcium
alkylhydroxybenzoate of Example A (32.3 mMol) and Example C (23.3 mMol) in a
total
amount of 0.2230 wt.%.
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Example 6
[00106] To formulation baseline 3 was added a mixture of both a calcium
alkylhydroxybenzoate of Example C (23.3 mMol) and an HOB sulfonate (31.7 mMol)
derived from a C20-24 NAO in a total amount of 0.2300 wt.%.
Comparative Example 4
[00107] To formulation baseline 3 was added a mixture of both a calcium
alkylhydroxybenzoate derived from a C20-28 NAO with a TBN of 135 on an oil
free basis
(24.1 mMol) and Comparative Example B (31.6 mMol) in a total amount of 0.2230
wt.%.
Comparative Example 5
[00108] To formulation baseline 3 was added a mixture of both a calcium
alkylhydroxybenzoate derived from a C2o-28NAO with a TBN of 135 on an oil free
basis
(27.7 mMol) and an HOB sulfonate (29.6 mMol) derived from a C20-24 NAO in a
total
amount of 0.2300 wt.%.
Baseline Formulation 4
[00109] A passenger car automotive 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 5W-40 finished oil:
(1) an ethylene carbonate post-treated bis-succinimide dispersant and borated
dispersant;
(2) 740 ppm in terms of phosphorus content, of a secondary zinc
dialkyldithiophosphatc;
(3) a mixture of a borated sulfonate, LOB sulfonate, and MOB phenate;
(4) Moly succinimide complex providing 90 ppm of molybdenum
(5) an alkylated diphenylamine and hindered phenol antioxidant;
(6) 5 ppm in terms of silicon content, of a foam inhibitor;
(7) 13.5 wt. % VII (additive) of Non-dispersant OCP and 0.3 wt. % PPD; and
(8) the remainder, a Group III base oil.
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Example 7
[00110] To formulation baseline 4 was added a calcium alkylhydroxybenzoate
of
Example A (27 mMol).
Comparative Example 6
[00111] To formulation baseline 4 was added a calcium alkylhydroxybenzoate
of
Comparative Example B (27 mMol).
ASTM D4684 Mini-Rotary Viscometer Test (MRV)
[00112] In this test, a test oil is first heated, and then cooled to test
temperature, in this
case ¨40 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.
[00113] The results of the MRV test for each of the lubricating oil
compositions are set
forth below in Table 4.
Table 4
Comp. Ex. 4 Ex. 5 Comp. Ex. 5 Ex. 6
<140 >350 <140
Yield Stress (-40 C) Pa >350
Frozen 33,800 Frozen 43,100
Viscosity (¨ 40 C) cP (<60,000)
Table 5
Comp. Ex. 6 Ex. 7
<35
Yield Stress (¨ 40 C) Pa >35
27,000 20,900
Viscosity (¨ 40 C) cP (<60,000)
24
CA 03068667 2019-12-30
WO 2019/003178
PCT/1132018/054806
[00114] From these examples it is clear that lubricating oils formulated
with an
alkylhydroxybenzoate detergent of the invention perform as well as or better
than
formulations containing alkyhydroxybenzoates which are not derived from
isomerized NAO
having from about 10 to about 40 carbon atoms.
