U.S. patent application number 17/144620 was filed with the patent office on 2021-05-13 for less corrosive organic compounds as lubricant additives.
This patent application is currently assigned to VANDERBILT CHEMICALS, LLC. The applicant listed for this patent is VANDERBILT CHEMICALS, LLC. Invention is credited to Brian M. CASEY, Vincent J. GATTO.
Application Number | 20210139806 17/144620 |
Document ID | / |
Family ID | 1000005370354 |
Filed Date | 2021-05-13 |
United States Patent
Application |
20210139806 |
Kind Code |
A1 |
CASEY; Brian M. ; et
al. |
May 13, 2021 |
LESS CORROSIVE ORGANIC COMPOUNDS AS LUBRICANT ADDITIVES
Abstract
A mixture of compounds, in which the mixture is a liquid at room
temperature, represented by the following formula: ##STR00001##
where R.sup.1 consists of a mixture of at least one unsaturated or
branched hydrocarbon chain and at least one saturated or unbranched
hydrocarbon chain, R.sup.2 is either a hydrogen atom or a
hydrocarbon chain, and m and n are independently from 1 to 5, when
used in a lubricating composition, being effective for friction and
wear reduction, while providing improved protection against copper
and lead corrosion in an engine.
Inventors: |
CASEY; Brian M.; (Norwalk,
CT) ; GATTO; Vincent J.; (Bradenton, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
VANDERBILT CHEMICALS, LLC |
NORWALK |
CT |
US |
|
|
Assignee: |
VANDERBILT CHEMICALS, LLC
NORWALK
CT
|
Family ID: |
1000005370354 |
Appl. No.: |
17/144620 |
Filed: |
January 8, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
16415535 |
May 17, 2019 |
10947473 |
|
|
17144620 |
|
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|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 133/16 20130101;
C10N 2030/12 20130101; C10M 2215/28 20130101; C10M 133/56 20130101;
C10N 2030/06 20130101 |
International
Class: |
C10M 133/56 20060101
C10M133/56; C10M 133/16 20060101 C10M133/16 |
Claims
1. A mixture of compounds, in which the mixture is a liquid at room
temperature, the mixture of compounds being the reaction product of
(a) a mixture of carboxylic acids or esters, wherein said mixture
comprises at least one first compound having a hydrocarbon chain
which is unsaturated or branched, and at least one second compound
having a hydrocarbon chain which is saturated and unbranched; (b)
one of (i) 2-aminoethylethanolamine, (ii)
alkyloxypropyl-1,3-diaminopropane, (iii)
alkyloxyethyl-1,3-diaminopropane, and (iv)
alkyloxypropyl-1,2-diaminoethane; and (c) glycidol.
2. The mixture of claim 1, wherein (b) is
2-aminoethylethanolamine.
3. The mixture of claim 1, wherein (b) is
alkyloxypropyl-1,3-diaminopropane.
4. The mixture of claim 1, wherein (a) is coconut oil acid or an
ester of coconut oil acid and (b) is 2-aminoethyl-ethanolamine.
5. The mixture of claim 1, wherein (a) is coconut oil acid or an
ester of coconut oil acid and (b) is
alkyloxypropyl-1,3-diaminopropane.
6. A liquid composition of matter represented by the following
formula: ##STR00005## where R1 is an unsaturated or branched
hydrocarbon chain, R2 is either a hydrogen atom or a hydrocarbon
chain, and m and n are independently from 1 to 5.
7. The composition of matter of claim 6, wherein the composition is
one of:
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide;
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide;
N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]isostearamide;
and
N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]oleamide.
8. A mixture of compounds, in which the mixture is a liquid at room
temperature, the compounds of said mixture being represented by the
following formula: ##STR00006## wherein said mixture comprises at
least one first compound having a hydrocarbon chain which is
unsaturated or branched, and at least one second compound having a
hydrocarbon chain which is saturated and unbranched; and where, R2
is either a hydrogen atom or a hydrocarbon chain, and m and n are
independently from 1 to 5.
9. The mixture of compounds of claim 8, being one of:
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]cocoamide;
and
N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]cocoamide.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application of
U.S. Ser. No. 16/415,535, filed May 17, 2019, and claims priority
thereof under 35 U.S.C. 120.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] This invention involves the development of less corrosive,
high performing organic compounds, which are liquid at room
temperature, with applications as additives in lubricants.
Lubricants containing these compounds have demonstrated improved
performance with respect to friction reduction, wear protection,
and copper and lead corrosion. In particular, the compounds of the
invention are
N-[3-[(2,3-dihydroxypropyl)(3-alkoxypropyl)amino]propyl]alkylamides,
and unsaturated or branched
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-alkylamides.
[0003] The claimed compounds represent a new class of additives
capable of meeting or exceeding the frictional and wear performance
of traditional additives while significantly reducing the severity
of the observed copper and lead corrosion. This inventive class of
compounds is particularly useful in both passenger car motor oil
and heavy-duty diesel engine oil applications where high
performing, more durable friction modifier and/or anti-wear
additives are required in terms of oxidative and hydrolytic
stability.
Discussion of the Prior Art
[0004] In the prior art, DE106196 and JP35012097 generally relate
to this class of compounds. However, neither unsaturated nor
branched examples of
N-[2-[(2,3-dihydroxy-propyl)(2-hydroxyethyl)amino]ethyl]-alkylamides
are contemplated; nor is there a discussion of
N-[3-[(2,3-dihydroxypropyl)(3-alkoxypropyl)amino]propyl]alkylamides.
Furthermore, neither DE1061966 nor JP35012097 contemplated use of
this class of compounds in lubricants as additives for friction
modification or wear protection.
[0005] DE 1061966 describes preparation of related 2,3-dihydroxy
compounds by reacting intermediate alkylamide,
N-[2-[(2-hydroxyethyl)amino]ethyl]- with .alpha.-chlorohydrin or
epichlorohydrin. This process can require the use of caustic bases
and generates halogenated waste. In the invention presented herein,
intermediate alkylamide amines were reacted instead with glycidol
in the presence of ethanol. These reactions benefit from being
completely atom economical and generate no waste. The ethanol can
be separated from the reaction by simple distillation and recycled
into the process. The reference teaches shampoo compositions which
comprise a component (a) being a quaternary ammonium salt of an
acyl derivative of non-aromatic carboxylic acids. Specifically,
intermediate compounds are created based on lauryl and stearyl
amides (which are saturated, unbranched) (examples 3, 7) which are
described in the reference as being pastes or paste-like solids
[0006] U.S. Pat. No. 5,397,486 teaches a reaction in which the
glycidol adducts differ from those used in the reaction to form the
inventive compounds. This reference uses glycidol adducts where X
is oxygen, sulfur, or nitrogen and R is a hydrocarbyl radical
containing 4-50 carbon atoms, the following formula
##STR00002##
[0007] The inventive class of compounds are chemically distinct and
outside the class described in U.S. Pat. No. 5,397,486. In
addition, U.S. Pat. No. 5,397,486 describes lubricant compositions
containing the above class of compounds as silver wear inhibiting
additives specifically for applications in diesel engines having
silver-surfaced engine parts. U.S. Pat. No. 9,464,252 teaches
glycidol adducts but does not contemplate their role in terms of
friction modifier performance, general wear protection, or impact
on copper and lead corrosion.
[0008] U.S. Pat. Nos. 5,560,853, 5,672,727, 9,321,976, 9,464,252
teach reactions in which the glycidol adducts differ from those
used in the reaction to form the inventive compounds. The inventive
class of compounds are chemically distinct and outside the class
described in these patents.
SUMMARY OF THE INVENTION
[0009] The class of compounds in the present invention may be a
mixture of compounds represented in Formula I:
##STR00003##
wherein at least one first compound has a hydrocarbon chain R1
which is unsaturated or branched, and at least one second compound
having a hydrocarbon chain R1 which is saturated and unbranched;
and where, R2 is either a hydrogen atom or a hydrocarbon chain, and
m and n are independently from 1 to 5, preferably 2 or 3.
[0010] It is important that the resulting product be a liquid. For
this reason, the preferred compound mixtures are limited to
hydrocarbon chains which are either unsaturated or are branched (or
in a mixture based on biological fatty acids, at least one of the
components is unsaturated or branched). It was surprising for the
inventors that this limitation, which is found in the exemplified
oleic, isostearic, and coco acid derivatives, resulted in desirable
liquid products. This is particularly unexpected given that
examples 3, 7 in DE 1061966 cover generally the same carbon chain
lengths yet result in pastes. It would be clear to those skilled in
the art that a liquid at room temperature is desired over a
non-liquid, particularly a paste which is difficult to handle.
[0011] This class of compounds can be prepared via General Reaction
Scheme I:
##STR00004##
[0012] In the first step, carbonyl-containing compounds such as
carboxylic acids, carboxylic acid esters, or triglycerides are
reacted with a mixed primary/secondary amine-containing compound to
form a secondary amide. In the second step, the secondary amide
intermediate is reacted further with glycidol to furnish the final
product described in Formula I. The second step can be performed in
the presence of a protic solvent such as methanol or ethanol to
improve the reaction efficiency.
[0013] As highlighted above, the class of compounds in this
invention may also be described as mixtures of the reaction
products of (a) carboxylic acids or esters or triglycerides, (b) a
mixed primary/secondary amine-containing compound, and (c)
glycidol. Non-limiting examples of the reaction products involved
in this invention include the following: [0014]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]lauramide
[0015]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]myristamide
[0016]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]palmitamide
[0017]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]stearamide
[0018]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearami-
de [0019]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]myristole-
amide [0020]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]palmitoleamide
[0021]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide
[0022]
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]linoleamide
[0023]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]la-
uramide [0024]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]myristami-
de [0025]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-
palmitamide [0026]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]stearamid-
e [0027]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]i-
sostearamide [0028]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]myristole-
amide [0029]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]palmitole-
amide [0030]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]oleamide
[0031]
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]li-
noleamide [0032]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]lauramide
[0033]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]myristam-
ide [0034]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]palmi-
tamide [0035]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]stearamide
[0036]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]isostear-
amide [0037]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]myristoleamide
[0038]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]palmitol-
eamide [0039]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]oleamide
[0040]
N-[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]linoleamide
[0041]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]lauramid-
e [0042]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]myrista-
mide [0043]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]palmitamide
[0044]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]stearami-
de [0045]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]isoste-
aramide [0046]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]myristoleamide
[0047]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]palmitol-
eamide [0048]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]oleamide
[0049]
N-[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]linoleamide
[0050]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]lauramid-
e [0051]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]myrista-
mide [0052]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]palmitamide
[0053]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]stearami-
de [0054]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]isoste-
aramide [0055]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]myristoleamide
[0056]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]palmitol-
eamide [0057]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]oleamide
[0058]
N-[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]linoleamide
[0059]
N-[2-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]ethyl]oleamide
[0060]
N-[3-[(2,3-dihydroxypropyl)(2-decyloxyethyl)amino]propyl]oleamide
[0061]
N-[2-[(2,3-dihydroxypropyl)(3-hydroxypropyl)amino]ethyl]oleamide
[0062]
N-[3-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]propyl]oleamide
[0063]
N-[2-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]ethyl]isosteara-
mide [0064]
N-[3-[(2,3-dihydroxypropyl)(2-decyloxyethyl)amino]propyl]isostearamide
[0065]
N-[2-[(2,3-dihydroxypropyl)(3-hydroxypropyl)amino]ethyl]isostearam-
ide [0066]
N-[3-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]propyl]isostea-
ramide
DETAILED DESCRIPTION OF THE INVENTION
[0067] The following two-step procedure is a representative example
for the preparation of the class of compounds described in the
present invention: 664 mmol of oleic acid is added to a 3-neck
flask fitted with a temperature probe, mechanical stirrer, and
distillation trap fitted with a condenser. To the flask is added
664 mmol of 2-aminoethyl-ethanolamine and the reaction is placed
under a nitrogen atmosphere. The reaction is heated to 150.degree.
C. and the generated water is collected in the distillation trap.
After heating for approximately 6 hrs, the reaction is cooled and
the product amide is used directly in the next step without
purification.
[0068] 271 mmol of the product from the previous step is added to a
3-neck flask fitted with a temperature probe and mechanical
stirrer. 275 mL of ethanol is added to the flask and a reflux
condenser is attached. A solution consisting of 258 mmol of
glycidol in 70 mL of ethanol is prepared and transferred to an
addition funnel with a nitrogen inlet attached atop the reflux
condenser. The reaction is placed under nitrogen atmosphere and
heated to reflux (approximately 80.degree. C.). The solution of
glycidol is added dropwise to the flask over 30 min. After the
addition is complete, the reaction is refluxed for an additional 6
hrs. The reaction was concentrated via rotary evaporation until all
the ethanol is removed to yield the desired product.
[0069] In carrying out the above reactions, a variety of starting
materials may be used as depicted in General Reaction Scheme I. In
the first step, the carbonyl-containing compound such as a
carboxylic acid, carboxylic acid ester, triglyceride, or mixtures
thereof may be used. For carboxylic acids, the R.sup.1 group
consisting of 1 to 21 carbon atoms can be a linear, cyclic, or
branched saturated hydrocarbon or an unsaturated and/or
polyunsaturated hydrocarbon or mixtures thereof. For carboxylic
acid esters, the R.sup.1 group consisting of 1 to 21 carbon atoms
can be a linear, cyclic, or branched saturated hydrocarbon or an
unsaturated and/or polyunsaturated hydrocarbon or mixtures thereof.
When using carboxylic acids or carboxylic acid esters, it is
important in the current invention for one of the components to
contain either an unsaturated or branched hydrocarbon chain. For
triglycerides, the R.sup.1 group consisting of 1 to 21 carbon atoms
can be a linear, cyclic, or branched saturated hydrocarbon or an
unsaturated and/or polyunsaturated hydrocarbon or mixtures thereof.
For the reaction of a carboxylic acid or carboxylic acid ester with
the primary amine-containing compound, the reaction stoichiometry
is typically 1.0 mole of carboxylic acid or carboxylic acid ester
to 1.0 mole of the primary amine-containing compound to produce the
desired secondary amide. Slight excesses or the carboxylic acid or
carboxylic acid ester, or the primary amine-containing compound may
be used but are generally not necessary nor preferred. Preferred
carboxylic acid esters are fatty acid methyl esters (FAME's) and
fatty acid ethyl esters, also referred to as biodiesel. Sources of
biodiesel are the fatty oils described below. For the reaction of a
triglyceride with the primary amine-containing compound, the
reaction stoichiometry can be varied such that 1.0 mole of
triglyceride is reacted with 1.0 to 3.0 mole of the primary
amine-containing compound to produce the desired secondary amide
and/or a mixture of the desired secondary amide with the
corresponding mono- and dialkylglycerates. The carbon chains in the
above examples of carbonyl-containing compounds can be derived from
fatty oils such as coconut oil, hydrogenated coconut oil, fish oil,
hydrogenated fish oil, tallow, hydrogenated tallow, corn oil,
rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil,
safflower oil, sesame oil, sunflower oil, canola oil, and soy bean
oil. For the mixed primary/secondary amine-containing compound, the
R.sup.2 group can be a hydrogen atom or a linear, cyclic, or
branched hydrocarbon chain containing 1 to 20 carbon atoms or
mixtures thereof and the number of methylene spacer groups (n and
m) can vary from 1 to 5.
[0070] The following examples were prepared using the
representative procedure provided above. All resulting products are
liquid at room temperature being about 20-22 degrees Celsius:
Example 1 (Ex. 1)
[0071] The preparative procedure for
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]oleamide
was identical to the representative procedure.
Example 2 (Ex. 2)
[0072] The preparative procedure for
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]-propyl]oleamide
was identical to the representative procedure except that
isotridecyloxypropyl-1,3-diaminopropane was used in place of
2-aminoethylethanolamine.
Example 3 (Ex. 3)
[0073] The preparative procedure for
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-cocoamide
was identical to the representative procedure except that coconut
oil methyl esters were used in place of oleic acid. This example
was a liquid at room temperature but formed a semi-solid gel when
cooled further. The material liquefied with gentle heating.
Example 4 (Ex. 4)
[0074] The preparative procedure for
N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]-propyl]cocoamid-
e was identical to the representative procedure except that coconut
oil methyl esters were used in place of oleic acid and
isotridecyloxypropyl-1,3-diaminopropane was used in place of
2-aminoethylethanolamine.
Example 5 (Ex. 5)
[0075] The preparative procedure for
N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-isostearamide
was identical to the representative procedure except that
isostearic acid was used in place of oleic acid.
[0076] The following compounds are included as comparative examples
to the invention disclosed herein:
Comparative Example 1 (CEx. 1)
[0077] Glycerol monooleate (HiTEC.RTM. 7133 from Afton
Chemical)
Comparative Example 2 (CEx. 2)
[0078] A commercial organic friction modifier comprised of the
products of the reaction of 1.0 mole of fatty oil having 12 or more
carbon atoms and 1.0-2.5 moles of diethanolamine.
[0079] Individual compounds from the inventive class of molecules
can be used as additives in lubricants for friction reduction
and/or supplemental wear protection at a treat rate from about
0.01-5.00 wt. %, preferably about 0.10-3.00%, and more preferably
about 0.20-2.00%, and still more preferably about 0.40-1.00%, as
weight percentage of the overall lubricating composition.
Furthermore, these compounds can be used in combination with other
additives such as dispersants, detergents, viscosity modifiers,
antioxidants, other friction modifiers, anti-wear agents, corrosion
inhibitors, rust inhibitors, salts of fatty acids (soaps), and
extreme pressure additives.
[0080] Dispersants that may be used include polyisobutylene
mono-succinimide dispersants, polyisobutylene di-succinimide
dispersants, polypropylene mono-succinimide dispersants,
polypropylene di-succinimide dispersants, ethylene/propylene
copolymer mono-succinimide dispersants, ethylene/propylene
copolymer di-succinimide dispersants, Mannich dispersants,
dispersant antioxidant olefin copolymers, low molecular weight
ethylene propylene succimimide dispersants, carboxylic dispersants,
amine dispersants, boronated dispersants, and molybdenum containing
dispersants.
[0081] Detergents that may be used include neutral calcium
sulfonate detergents, neutral magnesium sulfonate detergents,
overbased calcium sulfonate detergents, overbased magnesium
sulfonate detergents, neutral calcium phenate detergents, neutral
magnesium phenate detergents, overbased calcium phenate detergents,
overbased magnesium phenate detergents, neutral calcium salicylate
detergents, neutral magnesium salicylate detergents, overbased
calcium salicylate detergents, overbased magnesium salicylate
detergents, sodium sulfonate detergents, and lithium sulfonate
detergents.
[0082] Any type of polymeric viscosity index modifier may be used.
Examples include polymers based on olefin copolymers (OCPs),
polyalkylmethacrylates (PAMAs), poly-isobutylenes (PIBs), styrene
block polymers (such as styrene isoprene, styrene butadiene), and
ethylene alpha-olefin copolymers.
[0083] Molybdenum-based friction modifiers may be used to
supplement or enhance the overall performance of the class of
compounds in this invention. Examples of the types of alternative
friction modifiers that may be used include molybdenum complexes
prepared by reacting a fatty oil, diethanolamine and a molybdenum
source, molybdate esters, mononuclear molybdenum dithiocarbamates,
dinuclear molybdenum dithiocarbamates, trinuclear molybdenum
dithiocarbamates, sulfurized oxymolybdenum dithiocarbamates, sulfur
and molybdenum containing compounds, amine and molybdenum
containing compounds, molybdenum phosphorodithioates, sulfurized
oxymolybdenum dithiophosphates, tetraalkylammonium thiomolybdates,
molybdenum carboxylates, molybdenum xanthates, molybdenum
thioxanthates, imidazolium oxythiomolybdate salts, and quaternary
ammonium oxythiomolybdate salts. Typical treat rates for
molybdenum-based friction modifiers range from 50 ppm to 800 ppm of
delivered molybdenum to the finished lubricant formulation.
[0084] It is preferred that additives such as glycerol monooleate
and organic friction modifiers derived from fatty oils and
diethanolamine are not present because, as will be demonstrated,
these types of organic friction modifiers are highly corrosive to
copper and lead as determined by the high temperature corrosion
bench test (HTCBT, ASTM D6594). Accordingly, the invention also
comprises lubricating composition which are free of glycerol
monooleate and organic friction modifiers derived from fatty oils
and diethanolamine.
[0085] Preferred anti-wear additives that may be used include
primary and/or secondary zinc dialkyldithiophosphate (ZDDP),
triphenylphosphorothioates, dialkylphosphoric acid amine salts,
monoalkylphosphoric acid amine salts, dialkyldithiophosphate
succinates, dithiophosphoric ester or carboxylic acids,
trialkylborate esters, borate esters of fatty acid derivatives, and
methylenebis(dibutyldithiocarbamate).
[0086] Preferred antioxidants that may be used include
dinonyldiphenylamine, monononyldiphenylamine, dioctyldiphenylamine,
monooctyldiphenylamine, butyloctyldiphenylamine,
monobutyldiphenylamine, dibutyldiphenylamine,
nonylatedphenyl-alpha-naphthylamine octylated
phenyl-alpha-naphthylamine, dodecylated
phenyl-alpha-naphthylamine,2,6-di-tert-butylphenol,
butylatedhydroxytoluene,4,4-methylenebis(2,6-di-tert-butylphenol),
octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate,
isotridecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate,
2-ethylhexyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate,
isooctyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate and
thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
[0087] Preferred corrosion and rust inhibitors that may be used
include ethoxylated phenols, alkenylsuccinic acids, polyalkylene
glycols, derivatives of benzotriazole, derivatives of tolutriazole,
derivatives of triazole, dimercaptothiadiazole derivatives, fatty
acid derivatives of 4,5-dihydro-1H-imidazole, neutral calcium
dinonylnaphthalene sulfonates, neutral zinc dinonylnaphthalene
sulfonates, and neutral alkaline earth sulfonates.
[0088] Preferred extreme pressure additives that may be used
include sulfurized isobutylene, sulfurized alpha-olefins, aliphatic
amine phosphates, aromatic amine phosphates, dimercaptothiadiazole
derivatives, zinc dialkyldithiocarbamates, dialkylammonium
dialkyldithiocarbamates, and antimony dialkyldithiocarbamates.
[0089] Treat levels for all the above-mentioned additives can vary
significantly depending upon the application, additive solubility,
base fluid type, and finished fluid performance requirements.
Typical treat levels usually vary from 0.05 wt. % to 10.00 wt. %
based on the type of finished lubricant being developed. Base
fluids may include petroleum-based or synthetic stocks including
any fluid that falls into the API base stock classification as
Group I, Group II, Group III, Group IV, and Group V. Synthetic
fluids include poly-.alpha.-olefins, polyols, esters, bio-based
lubricants, and any combination of these. A lubricating base oil is
present in an amount of at least 80% of a total lubricating
composition.
[0090] The results of performance evaluations for the inventive
examples and the comparative examples are described in Examples
6-9. In Examples 6-8, inventive and comparative examples were
blended into an SAE 0W-20 passenger car motor oil (0W-20 PCMO) at
treat rates of 0.40-1.00 weight percent. This oil was fully
formulated except that it excluded an organic or organometallic
friction modifier (FM). In Example 9, inventive and comparative
examples were blended into a commercial, CK-4 equivalent SAE 15W-40
heavy duty diesel engine oil (15W-40 HDDEO) at a treat rate of 0.75
weight percent.
Example 6
Tribological Performance Testing by SRV
[0091] The test method described for ASTM D5707 (Standard Test
Method for Measuring Friction and Wear Properties of Lubricating
Grease Using a High-Frequency, Linear-Oscillation (SRV) Test
Machine) was followed to generate the performance data contained in
Table 1. The results presented in Table 1 clearly indicate that
both the inventive and comparative examples provided additional
wear protection as evidenced by lower wear volumes compared to the
0W-20 PCMO reference oil containing no FM. The improvements from
the inventive examples provided between 40-56% reductions in the
wear volume. In addition, inventive Ex. 2 and Ex. 4 provided a
modest improvement in the average coefficients of friction compared
to the 0W-20 PCMO reference oil.
TABLE-US-00001 TABLE 1 Tribological Performance Testing by SRV
(ASTM D5707) FM Treat Wear Volume Average Coefficient Additive Rate
(wt. %) (.mu.m.sup.3) of Friction 0W-20 PCMO 0 54,055 0.144 +CEx. 1
0.80 41,699 0.132 +CEx. 2 0.80 15,145 0.140 +Ex. 1 0.80 32,387
0.144 +Ex. 2 0.80 23,690 0.137 +Ex. 3 0.80 24,121 0.152 +Ex. 4 0.80
26,987 0.138
Example 7
Tribological Performance Testing by Four-Ball Wear
[0092] The test method described for ASTM D4172 B (Standard Test
Method for Wear Preventive Characteristics of Lubricating Fluid
(Four-Ball Method) was followed to generate the performance data
contained in Table 2. Under these test conditions, all four
inventive examples provided lower average coefficients of friction
compared to the 0W-20 PCMO reference oil containing no FM. In
addition, Ex. 2 and Ex. 4 provided improved wear protection as
indicated by reductions in the wear scar diameter.
TABLE-US-00002 TABLE 2 Tribological Performance Testing by
Four-Ball Wear (ASTM D4172 B) FM Treat Wear Scar Average
Coefficient Additive Rate (wt. %) Diameter (mm) of Friction 0W-20
PCMO 0 0.45 0.099 +CEx. 1 0.80 0.34 0.062 +CEx. 2 0.80 0.34 0.066
+Ex. 1 0.80 0.43 0.094 +Ex. 2 0.80 0.34 0.062 +Ex. 3 0.80 0.45
0.086 +Ex. 4 0.80 0.36 0.079
Example 8
Tribological Performance Testing by Mini Traction Machine (MTM)
[0093] Mini Traction Machine (MTM) was used to evaluate frictional
characteristics of lubricants in boundary and mixed lubrication
regime (Stribeck Curve) with "Ball on Disc" configuration. MTM
consists of a rotating 52100 steel ball pressed against an
independently rotating 52100 steel disc immersed in the lubricant.
The operating conditions are set by independently controlling the
rotational velocities of the shafts that drives the ball and the
disc, in order to obtain a particular combination of rolling speed
and slide to roll ratio, as well as by controlling the contact
force and the oil bath temperature. The test method parameters used
to generate the frictional performance data contained in Tables 3-6
from the Mini Traction Machine (MTM) are as follows: 35 N load
(.about.1 GPa), 50% slide:roll ratio, speed run from 3000 mm/s to
10 mm/s, 52100 steel. For each formulation, three Stribeck curves
were generated at 40.degree. C., 60.degree. C., 80.degree. C.,
100.degree. C., 120.degree. C., and 140.degree. C. The average
value from the three runs was reported at each temperature.
[0094] Table 3 demonstrates the improvements in the boundary
coefficients of friction for the inventive examples compared to the
0W-20 PCMO reference oil containing no FM. In particular, once the
temperature is at or above 80.degree. C., all five inventive
examples provided lower boundary coefficients. Most notably,
inventive Ex. 1 had the lowest boundary coefficient of friction at
temperatures of 60.degree. C. and above for all of the additives
evaluated. Table 4 contains the results for the Stribeck
Coefficients obtained for the oils at each temperature. For
temperatures at or above 100.degree. C., all inventive examples
significantly improved the frictional performance of the oil
compared to the formulation containing no FM. Of note, both
inventive Ex. 1 and 5 provided lower Stribeck Coefficients at
temperatures at or above 60.degree. C. than the reference oil
without friction modifier and oils containing either comparative
example. Similar to the frictional data in the boundary lubrication
regime, the oil containing inventive Ex. 1 provided significantly
lower Stribeck Coefficients than every other friction modifier
additive evaluated at temperatures from 80-140.degree. C. These
results indicate that inventive Ex. 1 not only improves the
frictional performance in the boundary lubrication regime but also
into the mixed and elastohydrodynamic regimes.
TABLE-US-00003 TABLE 3 Tribological Performance Testing by MTM FM
Treat Boundary Coefficient of Friction* at Specified Temperature
Additive Rate (wt %) 40.degree. C. 60.degree. C. 80.degree. C.
100.degree. C. 120.degree. C. 140.degree. C. 0W-20 PCMO 0 0.076
0.094 0.113 0.128 0.127 0.128 +CEx. 1 0.80 0.091 0.095 0.090 0.090
0.088 0.077 +CEx. 2 0.80 0.102 0.107 0.110 0.104 0.103 0.105 +Ex. 1
0.80 0.086 0.093 0.090 0.086 0.079 0.075 +Ex. 2 0.80 0.089 0.098
0.100 0.097 0.098 0.098 +Ex. 3 0.80 0.084 0.110 0.101 0.109 0.098
0.086 +Ex. 4 0.80 0.092 0.103 0.106 0.100 0.096 0.093 +Ex. 5 0.80
0.079 0.096 0.103 0.097 0.089 0.082 *Reported coefficients are the
average of three runs. Boundary coefficient is the coefficient of
friction at a speed of 10 mm/s.
TABLE-US-00004 TABLE 4 Tribological Performance Testing by MTM FM
Treat Stribeck Coefficient* at Specified Temperature Additive Rate
(wt. %) 40.degree. C. 60.degree. C. 80.degree. C. 100.degree. C.
120.degree. C. 140.degree. C. 0W-20 PCMO 0 0.135 0.141 0.167 0.219
0.268 0.278 +CEx. 1 0.80 0.142 0.156 0.168 0.180 0.191 0.181 +CEx.
2 0.80 0.160 0.158 0.159 0.159 0.172 0.198 +Ex. 1 0.80 0.145 0.138
0.133 0.134 0.134 0.138 +Ex. 2 0.80 0.148 0.152 0.161 0.172 0.197
0.218 +Ex. 3 0.80 0.141 0.169 0.176 0.196 0.201 0.196 +Ex. 4 0.80
0.149 0.152 0.164 0.170 0.178 0.184 +Ex. 5 0.80 0.134 0.135 0.140
0.144 0.157 0.163 *Stribeck coefficients are calculated by taking
the integration of the Stribeck curve at each individual
temperature.
[0095] Table 5 further demonstrates the improvements in the
boundary coefficients of friction for the inventive examples
compared to the 0W-20 PCMO reference oil that contains no friction
modifier. In these studies, formulations containing either
inventive or comparative examples at three different treat rates
were evaluated. From the data provided in Table 5, at temperatures
at or above 80.degree. C. all three inventive examples provided
lower boundary coefficients than the reference oil without any FM
even at the lowest treat rate (0.40 wt. %). Table 6 contains the
results for the Stribeck Coefficients obtained for the oils at each
temperature and treat rate. Again, once operating temperatures were
at or above 80.degree. C., all three inventive examples at each
treat rate demonstrated improved friction compared to the 0W-20
reference oil containing no FM as evidenced by lower Stribeck
Coefficients. As with the data shown in Table 4 above, formulations
containing inventive Ex. 1 demonstrated exceptional friction
reduction especially at higher operating temperatures and treat
rates. In particular, inventive Ex. 1 provided the lowest observed
Stribeck Coefficients for any of the additives evaluated from
100-140.degree. C. at the highest treat rate. These data in Tables
5 and 6 again indicate that inventive Ex. 1 not only improves the
frictional performance in the boundary lubrication regime but also
into the mixed and elastohydrodynamic regimes across a range of
treat rates.
TABLE-US-00005 TABLE 5 Tribological Performance Testing by MTM at
Additional Treat Rates FM Treat Boundary Coefficient of Friction*
at Specified Temperature Additive Rate (wt. %) 40.degree. C.
60.degree. C. 80.degree. C. 100.degree. C. 120.degree. C.
140.degree. C. 0W-20 PCMO 0 0.076 0.094 0.113 0.128 0.127 0.128
+CEx. 1 0.40 0.078 0.086 0.085 0.077 0.074 0.064 +CEx. 2 0.40 0.092
0.101 0.095 0.089 0.086 0.105 +Ex. 1 0.40 0.091 0.096 0.098 0.092
0.085 0.080 +Ex. 2 0.40 0.088 0.102 0.104 0.100 0.097 0.093 +Ex. 5
0.40 0.088 0.104 0.111 0.108 0.100 0.089 +CEx. 1 0.60 0.072 0.075
0.078 0.076 0.072 0.067 +CEx. 2 0.60 0.094 0.102 0.097 0.094 0.090
0.082 +Ex. 1 0.60 0.091 0.098 0.098 0.090 0.083 0.084 +Ex. 2 0.60
0.084 0.098 0.105 0.104 0.099 0.091 +Ex. 5 0.60 0.097 0.106 0.109
0.104 0.098 0.092 +CEx. 1 1.00 0.079 0.083 0.082 0.077 0.075 0.071
+CEx. 2 1.00 0.086 0.093 0.098 0.093 0.081 0.085 +Ex. 1 1.00 0.087
0.094 0.096 0.086 0.077 0.069 +Ex. 2 1.00 0.089 0.095 0.103 0.098
0.094 0.092 +Ex. 5 1.00 0.092 0.101 0.103 0.100 0.094 0.086
*Reported coefficients are the average of three runs. Boundary
coefficient is the coefficient of friction at a speed of 10
mm/s.
TABLE-US-00006 TABLE 6 Tribological Performance Testing by MTM at
Additional Treat Rates FM Treat Rate Stribeck Coefficient* at
Specified Temperature Additive (wt. %) 40.degree. C. 60.degree. C.
80.degree. C. 100.degree. C. 120.degree. C. 140.degree. C. 0W-20
PCMO 0 0.135 0.141 0.167 0.219 0.268 0.278 +CEx. 1 0.40 0.135 0.138
0.146 0.155 0.159 0.148 +CEx. 2 0.40 0.142 0.149 0.157 0.162 0.170
0.202 +Ex. 1 0.40 0.139 0.143 0.154 0.161 0.168 0.177 +Ex. 2 0.40
0.146 0.148 0.157 0.166 0.181 0.195 +Ex. 5 0.40 0.145 0.151 0.167
0.181 0.195 0.201 +CEx. 1 0.60 0.129 0.126 0.130 0.137 0.143 0.139
+CEx. 2 0.60 0.143 0.155 0.162 0.173 0.185 0.180 +Ex. 1 0.60 0.148
0.143 0.144 0.144 0.146 0.153 +Ex. 2 0.60 0.143 0.143 0.155 0.165
0.178 0.191 +Ex. 5 0.60 0.154 0.154 0.157 0.160 0.169 0.184 +CEx. 1
1.00 0.132 0.129 0.135 0.141 0.150 0.145 +CEx. 2 1.00 0.133 0.132
0.137 0.144 0.139 0.148 +Ex. 1 1.00 0.145 0.137 0.137 0.129 0.122
0.118 +Ex. 2 1.00 0.145 0.142 0.149 0.163 0.168 0.186 +Ex. 5 1.00
0.147 0.143 0.142 0.142 0.144 0.153 *Stribeck coefficients are
calculated by taking the integration of the Stribeck curve at each
individual temperature.
Example 9
Copper and Lead Corrosion Testing by High Temperature Corrosion
Bench Test (HTCBT)
[0096] The test method described for ASTM D6594 (Standard Test
Method for Evaluation of Corrosiveness of Diesel Engine Oil at
135.degree. C.) was followed to generate the copper and lead
corrosion data contained in Table 7. For API CK-4 category and
equivalent oils, the limits for passing the HTCBT are 20 ppm
maximum for copper, 120 ppm maximum for lead, and a 3 maximum
copper rating. From the data presented in Table 7, the inventive
examples provide significant improvements over the comparative
examples with respect the copper and lead corrosion. The data
clearly indicate that the inclusion of CEx. 1 as an FM additive in
the 15W-40 HDDEO results in a significant amount of both copper and
lead corrosion. The formulation containing CEx. 1, which is a
purely ester-based additive, fails for copper corrosion and
severely fails for lead corrosion. Alternatively, CEx. 2 is a
mixture of both amide- and ester-based compounds. For CEx. 2, the
oil now passes for copper corrosion. While the oil containing CEx.
2 still results in a severe failure for lead corrosion, the
observed lead values have been reduced over 70%. The inventive
examples are purely amide-based materials. For Ex. 1, the
formulation passes for copper and is a borderline fail for lead
corrosion. However, formulations containing either inventive Ex. 2
or Ex. 5 pass for both copper and lead corrosion and also match the
copper rating for the reference 15W-40 HDDEO. Inventive Ex. 2 and
Ex. 5 compared to CEx. 1 represent a 75% reduction in the copper
corrosion and nearly a 90% reduction in the lead corrosion. In
addition, inventive Ex. 2 and Ex. 5 benefit from more than a 60%
reduction in the lead corrosion compared to CEx. 2.
TABLE-US-00007 TABLE 7 Copper and Lead Corrosion Testing by HTCBT
(ASTM D6594) FM Treat Additive Rate (wt. %) Cu (ppm)* Cu Rating Pb
(ppm)* 15W-40 HDDEO 0 6.0 1b 7.5 +CEx. 1 0.75 40.0 2e 925.0 +CEx. 2
0.75 6.0 1b 270.0 +Ex. 1 0.75 14.5 1b 145.0 +Ex. 2 0.75 10.0 1b
103.5 +Ex. 5 0.75 11.0 1b 103.0 *Average of at least two runs
[0097] The results of the frictional performance, wear protection,
and corrosion testing demonstrate that the inventive examples
represent a new class of additives capable of meeting or exceeding
the frictional and wear performance of traditional additives while
significantly reducing the severity of the observed copper and lead
corrosion.
* * * * *