Note: Descriptions are shown in the official language in which they were submitted.
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LUBRICATING ENGINE OIL COMPOSITIONS CONTAINING DE ______ lERGENT
COMPOUNDS
This application claims the benefit of and priority to U.S. Provisional
Application Ser. No.
62/527,211, filed June 30, 2017.
BACKGROUND OF THE DISCLOSURE
100011 Neutral and 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 and corrosion and extending engine
life. Detergents
are utilized in lubricants for these benefits, but there are drawbacks to
their use as well.
Detergents are known to be detrimental to friction performance. Increased
friction is
associated with decreased fuel economy so this can be a drawback as fuel
economy
improvement is important for environmental and cost saving reasons.
100021 A major challenge in engine oil formulation is developing
lubricating oil
compositions which simultaneously achieve wear control and inhibits corrosion,
while also
achieving improved fuel economy. Surprisingly, it has been found that
lubricants formulated
with alkylhydroxybenzoate detergents derived from isomerized normal alpha
olefins show
improvements in oxidation reduction, corrosion inhibition and friction
performance.
SUMMARY OF THE DISCLOSURE
100031 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. an alkylhydroxybenzoate compound derived from Cio-Cao isomerized normal
alpha olefins, wherein the 1BN of the alkylhydroxybenzoate detergents from
to 300 mgKOH/gm on an oil-free basis.
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, and
2
b. an alkylhydroxybenzoate compound derived from Cw-Caoisomerized normal
alfa olefins, wherein the TBN of the alkylhydroxybenzoate compound is 10 -
300 mgKOH/gm on an oil-free basis.
[0003a] In accordance with another aspect, there is use of an
alkylhydroxybenzoate
detergent derived from Cio -C40 isomerized normal alpha olefms, wherein the
Total Base
Number (TBN) of the alkylhydroxybenzoate detergent determined in accordance
with ASTM
D2896 is from 10 to 300 mgKOH/gm on an oil-free basis, and wherein the
alkylhydroxybenzoate detergent is a Ca alkylhydroxybenzoate detergent, in a
lubricating oil
composition comprising an oil of lubricating viscosity in excess of 50 weight
% of the
composition, and wherein the lubricating oil composition comprises 0.01 to 2.0
wt.% in terms
of Ca content of the alkylhydroxybenzoate, to reduce friction in an engine
lubricated with the
lubricating oil composition, wherein friction performance is determined in
accordance with
the Mini-Traction Machine (MTM) bench test or obtained using a P1Mt TE-77 High
Frequency Friction Machine.
DETAILED DESCRIPTION OF THE DISLCOSURE
100041 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.
100051 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
[0006] 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.
[0007] A "major amount" means in excess of 50 weight % of a composition.
Date Recue/Date Received 2023-02-28
2a
[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.
100121 The abbreviation "ppm" means parts per million by weight, based on
the total
weight of the lubricating oil composition.
[0013] Total base number (TBN) was determined in accordance with ASTM
D2896.
[0014] High temperature high shear (HTHS) viscosity at 150 C was determined
in
accordance with ASTM D4863.
[0015] Kinematic viscosity at 100 C (KW:K) was determined in accordance
with
ASTM D445.
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[0015] Cold Cranking Simulator (CCS) viscosity at -35 C was determined in
accordance with ASTM D5293.
[0016] Noack volatility was determined in accordance with ASTM D5800Metal -
The term "metal" refers to alkali metals, alkaline earth metals, or mixtures
thereof.
[0017] 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.
[0018] 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.
[0019] 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.
[0020] All ASTM standards referred to herein are the most current versions
as of the
filing date of the present application.
[0021] In one aspect, the present disclosure is directed to a lubricating
oil composition
comprising:
(a) a major amount of an oil of lubricating viscosity, and
(b) a alkylhydroxybenzoate compound derived from Cio - Cu) isomerized normal
alpha olefins, wherein the alkylhydroxybenzoate compound has a 113N 10 - 300
mgKOH/gm on an oil-free basis.
[0022] In another aspect, the lubricating oil composition comprises a
molybdenum
compound.
[0023] In another aspect, provided is a method of lubricating an engine
comprising
lubricating said engine with lubricating oil composition comprising:
4
(a) a major amount of an oil of lubricating viscosity, and(b) a
alkylhydroxybenzoate compound derived from Cio-Coisomerized normal alfa
olefins, wherein the TBN of the alkylhydroxybenzoate compound is 10 - 300
mgKOH/gm on an oil-free basis.
100241 In another aspect, the present disclosure generally relates to
lubricating oil
compositions which 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.
[0025] Alkylhydroxybenzoate detergent derived from isomerized Normal Alpha
Olefin
(NAO)
[0026] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from C10-C40 isomerized NAO 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.
[0027] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
derived from Cio-C4oisomerized.NAO is a Ca alkylhydroxybenzoate detergent.
[0028] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent derived
from Cio-C40 isomerized NAO can be an alkylated hydroxybenzoate detergent. In
a another
embodiment, the detergent can be a salicylate detergent. In another
embodiment, the
detergent can be a carboxylate detergent.
[0029] In one aspect of the present disclosure, the alkylhydroxybenzoate
derived from
Cio-C40isomerized NAO having a TBN from 10 to 300 on an oil-free basis may be
prepared
as described in US Patent 8,893,499.
[0030] In one aspect of the present disclosure, the alkylhydroxybenzoate
detergent
having a TBN from 10 to 300 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 carbon
atoms per molecule, preferably from about 20 to about 24 carbon, or preferably
from about
20 to about 28 carbon atoms per molecule.
[0031] In one aspect of the present disclosure, the alkylhydroxybenzoate
derived from
C io-Cao isomerized NAO having a TBN from 10 to 300 on an active basis 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, and more preferably from about 0.12 to about
0.30.
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[0032] In one aspect of the present disclosure, the alkylhydroxybenzoate
derived from
Cio-C40isomerized NAO having a TBN from 10 to 300 on an active basis is made
from one
or more alkylphenols with an alkyl group derived from Cro-Caoisomerized NAO
and one or
more alkylphenols with an alkyl group different from Cio-Cao isomerized NAO.
[0033] In one aspect of the present disclosure, the isomerized NAO of the
alkylhydroxybenzoate has an isomerization level of about 0.16, and has from
about 20 to
about 24 carbon atoms.
[0034] In one aspect of the present disclosure, the isomerized NAO of the
alkylhydroxybenzoate has an isomerization level of about 0.26, and has from
about 20 to
about 24 carbon atoms.
[0035] 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 Cio-Coisomerized NAO having a TBN from 10 to 300 on an active basis,
preferably
0.1 to 1.0 wt. %, more preferably 0.05 to 0.5 wt. %, more preferably 0.1 to
0.5 wt.%.
[0036] In one aspect of the present disclosure, the lubricating oil
composition
comprising the alkylhydroxybenzoate derived from Cio-Cto isomerized NAO having
a TBN
from 10 to 300 on an oil-free basis 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.
[0037] In one aspect of the present disclosure, the lubricating oil
composition
comprising the alkylhydroxybenzoate derived from Cio-Cao isomerized NAO having
a TBN
from 10 to 300 on an oil-free basis is a functional fluid for automotive and
industrial
applications, such as transmission oil, hydraulic oil, tractor fluid, gear
oil, and the like.
[0038] In one aspect of the present disclosure, the lubricating oil
composition
comprising the alkylhydroxybenzoate derived from Cio-Cao isomerized NAO having
a 1BN
from 10 to 300 on an oil-free basis is a multi-grade oil or mono-grade oil.
[0039] In one aspect of the present disclosure, the lubricating oil
composition
comprising the alkylhydroxybenzoate derived from C10-C4o isomerized NAO having
a 1BN
from 10 to 300 on an oil-free basis lubricates crankcases, gears, as well as
clutches.
Or ganomolybdenum compound
100401 The organomolybdenum compound contains at least molybdenum, carbon
and
hydrogen atoms, but may also contain sulfur, phosphorus, nitrogen and/or
oxygen atoms.
Suitable organomolybdenum compounds include molybdenum dithiocarbamates,
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molybdenum dithiophosphates, and various organic molybdenum complexes such as
molybdenum carboxylates, molybdenum esters, molybdenum amines, molybdenum
amides,
which can be obtained by reacting molybdenum oxide or ammonium molybdates with
fats,
glycerides or fatty acids, or fatty acid derivatives (e.g., esters, amines,
amides). The term
"fatty" means a carbon chain having 10 to 22 carbon atoms, typically a
straight carbon chain.
[0041] In one embodiment, the molybdenum amine is a molybdenum-
succinimide
complex. Suitable molybdenum-succinimide complexes are described, for example,
in U.S.
Patent No. 8,076,275. These complexes are prepared by a process comprising
reacting an
acidic molybdenum compound with an alkyl or a1kenyl succinimide of a polyamine
of
structure (3) or (4) or mixtures thereof
=
= =
. R
(4).
.=
wherein R is a C24 to C350 (e.g., C70 to C128) alkyl or alkenyl group; R' is a
straight or
branched-chain alkylene group having 2 to 3 carbon atoms; x is 1 to 11; and y
is 1 to 10.
[0042] The molybdenum compounds used to prepare the molybdenum-
succinimide
complex are acidic molybdenum compounds or salts of acidic molybdenum
compounds. By
"acidic" is meant that the molybdenum compounds will react with a basic
nitrogen compound
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as measured by ASTM D664 or D2896. Generally, the acidic molybdenum compounds
are
hexavalent. Representative examples of suitable molybdenum compounds include
molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate,
potassium
molybdate and other alkaline metal molybdates and other molybdenum salts such
as
hydrogen salts, (e.g., hydrogen sodium molybdate), Mo0C14, MoO2Br2, Mo203C16,
and the
like.
[0043] The succinimides that can be used to prepare the molybdenum-
succinimide
complex are disclosed in numerous references and are well known in the art.
Certain
fundamental types of succinimides and the related materials encompassed by the
term of art
"succinimide" are taught in U.S. Patent Nos. 3,172,892; 3,219,666; and
3,272,746. The term
"succinimide" is understood in the art to include many of the amide, imide,
and amidine
species which may also be formed. The predominant product however is a
succinimide and
this term has been generally accepted as meaning the product of a reaction of
an alkyl or
alkenyl substituted succinic acid or anhydride with a nitrogen-containing
compound.
Preferred succinimides are those prepared by reacting a polyisobutenyl
succinic anhydride of
about 70 to 128 carbon atoms with a polyalkylene polyamine selected from
triethylenetetramine, tetraethylenepentamine, and mixtures thereof.
[0044] The molybdenum-succinimide complex may be post-treated with a
sulfur
source at a suitable pressure and a temperature not to exceed 120 C to provide
a sulfurized
molybdenum-succinimide complex. The sulfurization step may be carried out for
a period of
from about 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sources of sulfur
include elemental
sulfur, hydrogen sulfide, phosphorus pentasulfide, organic polysulfides of
formula R2Sr
where R is hydrocarbyl (e.g., Ci to Cu) alkyl) and x is at least 3, CI to CH)
mercaptans,
inorganic sulfides and polysulfides, thioacetamide, and thiourea.
[0045] The molybdenum compounds are used in an amount that provides at
least 50
ppm, at least 70 ppm, at least 90 ppm, at least 110 ppm, at least 130 ppm, at
least 150 ppm, or
at least 200 ppm (e.g., 50 to 1500 ppm, 70 to 1500 ppm, 90 to 1000 ppm, 110 to
1000 ppm,
130 to 1000 ppm, 150 to 1000 ppm, or 200 to 1000 ppm) by weight of molybdenum
to the
lubricating oil composition.
Friction Modifiers
[0046] The lubricating oil composition disclosed herein can comprise a
friction
modifier that can lower the friction between moving parts. Any friction
modifier known by a
person of ordinary skill in the art may be used in the lubricating oil
composition. Non-
limiting examples of suitable friction modifiers include fatty carboxylic
acids; derivatives
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(e.g., alcohol, esters, borated esters, amides, metal salts and the like) of
fatty carboxylic acid;
mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids;
derivatives (e.g.,
esters, amides, metal salts and the like) of mono-, di- or tri-alkyl
substituted phosphoric acids
or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-
alkyl substituted
amides and combinations thereof In some embodiments, the friction modifier is
selected
from the group consisting of aliphatic amines, ethoxylated aliphatic amines,
aliphatic
carboxylic acid amides, ethoxylated aliphatic ether amines, aliphatic
carboxylic acids,
glycerol esters, aliphatic carboxylic ester-amides, fatty imidazolines, fatty
tertiary amines,
wherein the aliphatic or fatty group contains more than about eight carbon
atoms so as to
render the compound suitably oil soluble. In some embodiments, the friction
modifier is a
fatty acid derivative. In some embodiments, the fatty acid derivative is a
fatty acid ester, a
borated fatty acid ester, or an amide. In other embodiments, the friction
modifier comprises
an aliphatic substituted succinimide formed by reacting an aliphatic succinic
acid or
anhydride with ammonia or a primary amine. The amount of the friction modifier
may vary
from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt. % to about 5 wt.
%, or from
about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating
oil composition.
Antiwear Agents
100471 Antiwear agents reduce wear of metal parts. Suitable anti-wear
agents include
dihydrocarbyl dithiophosphate metal salts such as zinc dihydrocarbyl
dithiophosphates
(ZDDP) of formula (Formula 1):
Zn[S¨P(=S)(ORI)(OR2)]2 Formula 1,
wherein le 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 RI 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., 1V-FR2) will be at least 5. The zinc
dihydrocarbyl
dithiophosphate can therefore comprise zinc dialkyl dithiophosphates. The zinc
dialkyl
dithiophosphate is a primary, secondary zinc dialkyl dithiophosphate, or a
combination thereof
100481 ZDDP 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 composition.
100491 In one embodiment, the lubricating oil composition containing the
magnesium
salicylate detergent described herein further comprises an antioxidant
compound. In one
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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 diphcnylamine antioxidant and a hindered phenol antioxidant.
Antioxidants
[0050] 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.
[0051] 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-ethy1-2,6-
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 IRGANOX L-135 from Ciba
and bis-
phenolic antioxidants such as 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-
methylenebis(2,6-di-
tert-butylphenol).
[0052] 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-naphthylarnine, N-(4-tert-octypheny1)-1-naphthylamine, and N-(4-
octylpheny1)-1-
naphthylamine.
[0053] Antioxidants may be present at 0.01 to 5 wt. % (e.g., 0.1 to 2 wt.
%) of the
lubricating oil composition,
Dispersants
[0054] 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-
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containing, ashless (metal-free) dispersants known to effective to reduce
formation of
deposits upon use in gasoline and diesel engines.
[0055] Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl
succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid,
hydroxycsters 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.
100561 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.
[0057] 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(C1-12CH2NH)1fl 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.
[0058] As is known in the art, the dispersants may be post-treated (e.g.,
with a
boronating agent or a cyclic carbonate).
[0059] Nitrogen-containing ashless (metal-free) dispersants are basic,
and contribute
to the 113N of a lubricating oil composition to which they are added, without
introducing
additional sulfated ash.
[0060] Dispersants may be present at 0.1 to 10 wt. % (e.g., 2 to 5 wt. %)
of the
lubricating oil composition.
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Additional Detergents
[0061] The lubricating oil composition of the present invention can
further contain
one or more overbased detergents having a TBN of 10-800, 10-700, 30-690, 100-
600, 150-
600, 150-500, 200-450 mg KOH/g on an actives basis.
[0062] In some embodiments, the detergents that may be used include oil-
soluble
sulfonate, 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 magnesium, which may both be present in detergents used
in a
lubricant, and mixtures of calcium and/or magnesium with sodium.
[0063] 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.
[0064] Overbased detergents may be low overbased, e.g., an overbased salt
having a
113N 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 TBN of a
medium overbased salt may be from about 100 to about 200. In another
embodiment, the
1BN 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 TBN of a high overbased salt may be from about 250 to about
800 on an
actives basis.
[0065] 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, hydroquinone,
pyrogallol,
cresol, and the like. The preferred hydroxyaromatic compound is phenol.
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[0066] 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.
[0067] 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
per molecule. In one embodiment, the normal alpha olefins are isomerized using
at least one
of a solid or liquid catalyst.
[0068] 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 isomerized olefins or mixtures thereof.
[0069] 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.
[0070] 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, xylene, 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
13
carbon atoms, preferably about 16 to 30 carbon atoms, and more preferably 20-
24 carbon
atoms per alkyl substituted aromatic moiety.
[0071] Metal salts of phenols and sulfurized phenols, which are sulfurized
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
products which are generally mixtures of compounds in which 2 or more phenols
are bridged
by sulfur containing bridges.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] 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.
[0076] 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.
Date Recue/Date Received 2023-02-28
14
[0077] 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.
[0078] The alkylphenols can be para-alkylphenols, meta-alkylphenols or
ortho
alkylphenols_ Since it is believed that p-allcylphenols 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 oitho 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 substituent 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-
hydxocarbyl
substituted phenols_
[0079] 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_
[0080] 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.
Additional Co-Additives
[0081] 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 Molter 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
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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.
[0082] 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.
[0083] 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.
[0084] 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.
[0085] 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 1ubr1cat1n2 viscosity
[0086] 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 concentiates as well as for making lubricating oil
compositions
therefrom, and may be selected from natural and synthetic lubricating oils and
combinations
thereof.
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100871 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.
[0088] 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-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.
[0089] 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.
[0090] 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 tripentaelythritol.
[0091] The base oil may be derived [loin 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.
[0092] 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
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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.
[0093] 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.
[0094] 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 1
Base Oil Properties
Group( Saturates", wt. % Sulfuro, wt. % Viscosity Index4
Group I <90 and/or >0.03 80 to <120
Group II >90 <0.03 80 to <120
Group III >90 <0.03 >120
Group IV Polyalphaolefins (PA0s)
Group V All other base stocks not included in Groups I, II, III or
IV
" Groups I-III are mineral oil base stocks.
(b) Determined in accordance with ASTM D2007.
(o Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM
D4927.
(d) Determined in accordance with ASTM D2270.
100951 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.
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100961 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 formula, 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.
100971 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, OW-8,
OW-12, OW-
16, OW-20, OW-26, OW-30, OW-40, OW-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
[0098] 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
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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.
[0099] 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. %.
[00100] 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
20
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.
1001011 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.
EXA1VIPLES
1001021 The following examples are intended for illustrative purposes only
and do not
limit in any way the scope of the present disclosure.
[00103] The isomerization level was measured by an NMR method.
Isomerization level (I) and NMR method
[00104] The isomerization level (I) of the olefin was deteimined by
hydrogen-1 (1H)
NMR_ The NMR spectra were obtained on a BrukerTM Ultrashield Plus 400 in
chlorofolin-d1
at 400 MHz using TopSpinTm 3.2 spectral processing software.
[00105] The isomerization level (I) represents the relative amount of
methyl groups (-
CH3) (chemical shift 0.30-1.01 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 (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.
Baseline Formulation 1
[00106] A 15W-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 mixture of a primary zinc dialkyldithiophosphate and a secondary zinc
dialkyldithiophosphate;
(3) a diphenylamine antioxidant;
(4) 45 ppm in terms of molybdenum content of a sulfur-containing molybdenum
succinimide; and
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(5) a foam inhibitor.
Baseline Formulation 2
[00107] A 15W-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 secondary zinc dialkyldithiophosphate;
(3) a diphenylamine antioxidants;
(4) 380 ppm in terms of molybdenum content of a sulfur-containing molybdenum
succinimide; and
(5) a foam inhibitor.
Baseline Formulation 3
[00108] A 15W-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 secondary zinc dialkyldithiophosphate;
(3) a diphenylamine antioxidant;
(4) 380 ppm in terms of molybdenum content of a sulfur-free molybdenum
succinimide; and
(5) a foam inhibitor.
Example A
[00109] An alkylated phenol and alkylated 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 available from CP Chem. The isomerization level of the
alpha olefin is
about 0,16. The resulting alkylated alkylhydroxybenzoate composition has a TBN
of about
225 mgKOH/gm and Ca content of 8 wt.% on an oil-free basis.
Example B
[00110] An alkylated phenol and alkylated 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 available from CP Chem. The isomerization level of the
alpha olefin is
about 0.16. The resulting alkylated alkylhydroxybenzoate composition has a
113N of about
120 mgKOH/gm and Ca content of 4.2 wt.% on an oil-free basis.
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Comparative Example A
[00111] An alkylated phenol and alkylated Ca alkylhydroxybenzoate were
prepared in
substantially the same manner as in U.S. Patent No. 8,030,258 using a C2o-28
normal alpha
olefin available from CP Chem. The resulting alkylated alkylhydroxybenzoate
composition
has a TBN of about 230 and Ca content about 8 wt.% on an oil-free basis.
Comparative Example B
[00112] An alkylated alkylhydroxybenzoate was prepared from an alkylphenol
with an
alkyl group derived from C14 - C18 normal alpha olefin and a TBN about 300
mgKOH/grn
and Ca content about 10.6 wt. % on an oil-free basis.
Comparative Example C
[00113] An alkylated alkylhydroxybenzoate was prepared from an alkylphenol
with an
alkyl group derived from C2o ¨ C28 normal alpha olefin and a 1BN about 115
mgKOH/grn
and Ca content about 4 wt. % on an oil-free basis.
Comparative Example D
[00114] A highly overbased Ca Sulfonate having a I BN about 700 mgKOH/gm
and
Ca content about 26 wt. % on an oil-free basis.
Example 1
[00115] To baseline formulation 1 was added 0.35 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Example A. The lubricating oil composition
has 0.21 wt%
of S, 0.1 wt% of P, and 1.3 wt% of ash.
Comparative Example 1
[00116] To baseline formulation 1 was added 0.35 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate detergent of Comparative Example A. The lubricating oil
composition
has 0.22 wt% of S, 0.1 wt% of P, and 1.3 wt% of ash.
Comparative Example 2
[00117] To baseline formulation 1 was added 0.35 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate of Comparative Example B. The lubricating oil composition
has 0.22
wt% of S, 0.1 wt% of P, and 1.3 wt% of ash.
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Example 2
[00118] To baseline formulation 2 was added 0.35 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate of Example A. The lubricating oil composition has 0.17
wt% of S,
0.07 wt% of P, and 1.3 wt% of ash.
Comparative Example 3
1001191 To baseline formulation 2 was added 0.35 wt.% in terms of Ca
content of a Ca
alkylhydroxybenzoate of Comparative Example B. The lubricating oil composition
has 0.16
wt% of S, 0.07 wt% of P, and 1.3 wt% of ash.
Example 3
1001201 To baseline formulation 3 was added 0.35 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Example A. The lubricating oil composition has 0.17
wt% of S,
0.07 wt% of P, and 1.3 wt% of ash.
Comparative Example 4
1001211 To baseline formulation 3 was added 0.35 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Comparative Example B. The lubricating oil composition
has 0.16
wt% of S. 0.07 wt% of P, and 1.3 wt% of ash.
1001221 Examples! to 3, and Comparative Examplesl to 4 were evaluated in
the
l'hOST MHT4 and HTCBT tests described below. Results are in Table 2.
TEOST MHT4
1001231 The ASTM D7097 thOST MHT4 test is designed to predict the deposit-
forming tendencies of engine oil in the piston ring belt and upper piston
crown area.
Correlation has been shown between the TEOST MI-1T procedure and the TU3MH
Peugeot
engine test in deposit formation. This test determines the mass of deposit
formed on a specially
constructed test rod exposed to repetitive passage of 8.5 g of engine oil over
the rod in a thin
film under oxidative and catalytic conditions at 285 deg C. Deposit-forming
tendencies of an
engine oil under oxidative conditions are determined by circulating an oil-
catalyst mixture
comprising a small sample (8.4 g) of the oil and a very small (0.1 g) amount
of an organo-
metallic catalyst. This mixture is circulated for 24 hours in the TEOST MHT
instrument over
a special wire-wound depositor rod heated by electrical current to a
controlled temperature of
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285 deg C at the hottest location on the rod. The rod is weighed before and
after the test.
Deposit weight of 35 mg is considered as pass/fail criteria.
HTCBT
1001241 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 and TEOST MHT4
HTCBT (lead in ppm) 1E0 ST MHT4
Example 1 6 25.7
Comparative Ex 1 32 25.2
Comparative Ex 2 68 74.6
Example2 14 11.8
Comparative Ex 3 104 33.4
Example 3 17 14.8
Comparative Ex 4 110 24.9
[00125] The Ca alkylhydroxybenzoate derived from Cm - C24 isomerized NAO
has
surprisingly better corrosion inhibition and deposit control performance than
the Ca
alkylhydroxybenzoate derived from non-isomerized NAO at equal Ca level. This
effect is
enhanced in the presence of an effective level of a molybdenum compound.
Baseline Formulation 4
[00126] A 5W-20 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 borated bis-succinimide dispersant;
(3) a mixture of a primary zinc dialkyldithiophosphate and a secondary zinc
dialkyldithiophosphate;
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(4) a mixture of molybdenum succinimide and diphenylamine antioxidants; and
(5) a foam inhibitor.
Example 4
[00127] To baseline formulation 4 was added 0.18 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Example A. The lubricating oil composition has 0.16
wt% of S,
0.077 wt% of P, and 0.75 wt% of ash.
Example 5
[00128] To baseline formulation 4 was added 0.18 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Example A and 68 ppm in terms of Boron content of a
borated
glycerol monooleate (Glymo) friction modifier. The lubricating oil composition
has 0.16 wt%
of S, 0.077 wt% of P, and 0.76 wt% of ash.
Comparative Example 8
[00129] To baseline formulation 4 was added 0.18 wt% in terms of Ca content
of a
highly overbased Ca sulfonate detergent and 68 ppm in terms of B content of a
borated
glycerol monooleate (Glymo) friction modifier. The lubricating oil composition
has 0.18
wt% of S, 0.077 wt% of P, and 0.75 wt% of ash.
Comparative Example 9
[00130] To baseline formulation 4 was added 0.18 wt% in terms of Ca content
of
Comparative Example D. The lubricating oil composition has 0.18 wt% of S,
0.077 wt% of P.
and 0.76 wt% of ash.
MTM TEST
[00131] Examples 4 to 5, and Comparative Examples 8 and 9 were tested for
friction
performance in a Mini-Traction Machine (MTM) bench test. The MTM is
manufactured by
PCS Instruments and operates with a ball (0.75 inches 8620 steel ball) loaded
against a
rotating disk (52100 steel). The conditions employ a load of approximately 10-
30 Newtons, a
speed of approximately 10-2000 mm/s and a temperature of approximately 125-150
C. In
this bench test, the boundary friction performance of a formulation under a
rolling/sliding
contact is measured by the low speed traction coefficient. The low speed
traction coefficient
is the average traction coefficient of the second Stribeck between 15 and
20mm/s. Lower low
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speed traction coefficients correspond to better boundary friction performance
of the oil.
Results are in Table 3.
[00132]
Table 3 - MTM Test
Low Speed Traction Coefficient
Example 4 0.1268
Example 5 0.0885
Comparative Example 8 0.1150
Comparative Example 9 0.1269
[00133] The Ca alkylhydroxybenzoate derived from C2o - C24 isomerized NAO
has
similar boundary friction performance to the highly overbased Ca Sulfonate at
equal Ca level.
However, the combination of the alkylhydroxybenzoate derived from C2o - C24
isomerized
NAO and a friction modifier has significantly better boundary friction
performance than the
combination of the highly overbased Ca Sulfonate and a friction modifier or
the
alkylhydroxybenzoate alone, indicating a synergistic effect between the
alkylhydroxybenzoate and the friction modifier.
Baseline Formulation 5
[00134] A railroad 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 mixture of phenate detergents
(3) a mixture of Moly succinimide and diphenylamine antioxidants;
(4) a friction modifier
(5) a foam inhibitor.
(6) a viscosity modifier
Example 6
[00135] To baseline formulation 5 was added0.05wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Example A.
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Comparative Example 10
[00136] To baseline formulation 5 was added 0.04wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Comparative Example A.
1001371 Example 6 and Comparative Example 10 were evaluated in the B2-7
Oxidation Test and the B72-2 Ah Silver Lubricity Test as described below.
B2-7 Test
[00138] The B2-7 test is an oxidation test with the following conditions:
Oxidatim 032)
Temp 149 C. (300E)
Duration 96 hr
Coupons Cu, 1e. Pb
Flow oxygen
Repienittbiag oil Al 48 hr (SO niL)
72 hr (50 .m1.)
Commons Trend daa flN, AN, pH and Pb ppm.
[00139] According to the B2-7 test, the oil to be tested is heated at 300
F for 96 hours
with bubbling of oxygen. Copper, iron and lead coupons are suspended in the
oil. Fifty
milliliter samples are taken at 48, 72 and 96 hours. The samples at 48 and 72
hours are
replenished with fresh oil. The oil test samples are evaluated for base
number, acid number,
pH and lead.
Comparative Example 10 and Example 6 of the invention were evaluated for Total
Base
Number (TBN) decrease. The results are in table 4.
Table 4¨ B2-7 Test
TBN D4739 Comparative Example 10 Example 6
Ohr 9.70 9,64
48hr 6.50 6.76
72 hr 6.21 6.49
96 hr 5.98 6.22
TBN decrease 3.72 3.42
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[00140] Higher numbers for IBN decrease indicate greater depletion of the
base in the
oil and are considered less favorable. An oil for extended use in a locomotive
diesel engine
will ideally retain TBN.
[00141] The results show that the Ca alkylhydroxybenzoate detergent derived
from Czo
- C24 isomerized NAO provide better BN retention when compared with the Ca
alkylhydroxybenzoate detergent derived from non-isomerized NAO, meaning better
protection of the engine.
Baseline Formulation 6
[00142] A 5W-30 lubricating oil composition was prepared that contained a
major
amount of a base oil of lubricating viscosity and the following additives:
(1) a borated bis-succinimide;
(2) an ethylene carbonate-treated bissuccinimide;
(3) a highly overbased Ca sulfonate detergent
(4) a mixture of a primary zinc dialkyldithiophosphate and a secondary zinc
dialkyldithiophosphate;
(5) a mixture of Moly succinimide and diphenylamine antioxidants;
(6) a friction modifier
(7) a foam inhibitor
(8) a pour point depressant
(9) a viscosity modifier
Example 7
[00143] To baseline formulation 6 was added 0.1 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Example B.
Comparative Example 11
[00144] To baseline formulation 6 was added 0.1 wt% in terms of Ca content
of a Ca
alkylhydroxybenzoate of Comparative Example C.
[00145] Example 7 and Comparative Example 11 were evaluated in the MRV test
as
described below.
MRV (Mini Rotary Viscometer)
The ASTM D4684 MRV test covers the measurement of the yield stress (0<Y<35
max) and
viscosity (60,000 cp max) of engine oils after cooling at controlled rates
over a period not
exceeding 45 h to a final test temperature between -10 and -40 C. In the MRV
test an engine
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oil sample is held at 80 C. and then cooled at a programmed cooling rate to a
final test
temperature. A low torque is applied to the rotor shaft to measure the yield
stress. A higher
torque is then applied to determine the apparent viscosity of the sample. The
viscosity
measurements are made at shear stress of 525 Pa over a shear rate of 0.4 to 15
s-1.
Table 5. MRV Test (&,-35C (ASTM D-4684)
Apparent Viscosity (cP) Yield Stress (Pa)
Example 7 43100 <175
Comparative 11 Frozen >350
[00146] The Ca alkylhydroxybenzoate derived from C2o - C24isomerized NAO
has
surprisingly better low temperature performance than the Ca
alkylhydroxybenzoate derived
from non-isomerized NAO at equal Ca level.
Baseline Formulation 7
[00147] A 5W-20 lubricating oil composition was prepared that contained a
major
amount of a base oil of lubricating viscosity and the following additives:
(1) a borated bis-succinimide;
(2) an ethylene carbonate-treated bissuccinimide;
(3) a mixture of a primary zinc dialkyldithiophosphate and a secondary zinc
dialkyldithiophosphate;
(4) a mixture of Moly succinimide and diphenylamine antioxidants;
(5) a friction modifier
(6) a foam inhibitor
(7) a pour point depressant
(8) a viscosity modifier
Example 8
(9) To baseline formulation 7 was added 0.06 wt% in terms of Ca content of a
Ca
alkylhydroxybenzoate of Example A and 0.12 wt% in terms of Ca content of
Comparative Example D
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Example 9
(10) To baseline formulation 7 was added 0.12 wt% in terms of Ca content
of a Ca alkylhydroxybenzoate of Example A and 0.06 wt% in terms of Ca
content of Comparative Example D
Comparative Example 12
(11) To baseline formulation 7 was added 0.18 wt% in terms of Ca content
of a Ca alkylhydroxybenzoate of Example A.
Comparative Example 13
(12) To baseline formulation 7 was added 0.18 wt% in terms of Ca content
of Comparative Example D.
(13) Example 8, 9 and Comparative Example 12 and13 were evaluated in
the 1'E 77 test as described below.
Flint TE 77 High Frequency Friction Machine
Boundary friction coefficient measurements for the Examples 8 and 9, and
Comparative
Examples 12 and 13 were obtained using a Flint TE-77 High Frequency Friction
Machine
(commercially available from Phoenix Tribology).
A 5mL sample of test oil was placed in the apparatus for each test. The TE-77
was run at 100
C and 56N of load was placed on the testing specimen. The reciprocating speed
was swept
from 10Hz to 1Hz, and coefficient of friction data was collected throughout
the test. The
friction coefficient measurements are shown in Table 6.
Table 6 P1Mt TE 77
Example 8 Example 9 Comp Example Comp Example
12 13
1 Hz 0.01 0.01 0.06 0.02
2 Hz 0.01 0.01 0.06 0.02
3 Hz 0.01 0.01 0.07 0.02
4 Hz 0.01 0.02 0.07 0.04
5 Hz 0.01 0.03 0.07 0.06
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6 Hz 0.02 0.05 0.08 0.08
7 Hz 0.05 0.07 0.08 0.10
8 Hz 0.07 0.08 0.08 0.12
9 Hz 0.09 0.09 0.09 0.13
Hz 0.10 0.08 0.08 0.14
Coefficient of friction data collected for these oils at reciprocating speeds
of 1
to 2 Hz are in a boundary friction regime.
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.
Based on the boundary friction regime results from Examples 8 and 9, it is
evident that there is synergistic effect when the alkylhydroxybenzoate derived
from
isomerized normal alpha olefin is used together with the overbased Ca
snlfonate.
Baseline Formulation 8
A 5W-30 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-treated bissuccinimide;
(2) a highly overbased Ca sulfonate detergent
(3) a secondary zinc dialkyldithiophosphate;
(4) a diphenylamine antioxidant
(5) a foam inhibitor
(6) a pour point depressant
(7) a viscosity modifier
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Example 10
(8) To baseline formulation 8 was added 0.2 wt% in terms of Ca content of a Ca
alkylhydroxybenzoate of Example A.
Comparative Example 13
(9) To baseline formulation 8 was added 0.2 wt% in terms of Ca content of a Ca
alkylhydroxybenzoate of Comparative Example B.
Sequence WA Test
The lubricating oil compositions of Example 1.0 and Comparative Example 13
were
evaluated for valve tram wear in a gasoline engine: Sequence IVA., A.STM D
6891,
Average cam wear (7 position average. wn). The passim, limit for this test is
90 p.m
maximum.
Table 7. Sequence IVA. Test
Example 10 Comp.
Example 13
Camshaft Wear (p.m) 67 96
1001481 The Ca
alkylhydroxybenzoate derived from C20 - C24 isomerized NAO has
surprisingly better valve tram wear performance than the Ca
alkylhydroxybenzoate derived
from non-isomerized NAO at equal Ca level.
