Note: Descriptions are shown in the official language in which they were submitted.
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1
s FRICTION REDUCING ADDITIVES >=OR FUE!_S AND LUBRICANTS
This invention is directed to alkylamines which have been reacted with
dialkylcarbonates andlor alkylene carbonates to form N-alkylalkylcarbamates
and N-
io alkylhydroxyalkylcarbamates and the use of the resulting products as
friction
reducing additives in fuels and tubes. More particularly, it is directed to
fuel and
lubricating compositions and concentrates containing such friction reducing
additives.
A major concern today is finding methods to reduce engine friction and fuel
is consumption in internal combustion engines which are safe for the
environment and
economically attractive. One means is to treat moving parts of such engines
with
lubricants containing friction reducing additives. Considerable work has been
done
in this area.
U.S. Patent No. 4,617,026 discloses the use of monocarboxylic acid ester of
2o trihydric alcohol, glycerol monooleate, as a friction reducing additive in
fuels and
lubricants promoting fuel economy in an internal combustion engine.
The use of fatty formamides is disclosed in U:S. Patent Nos. 4,789,493;
4,808,196; and 4,867,752.
The use of fatty acid amides is disclosed in U.S. Patent No. 4,280,916.
2s U.S. Patent No. 4,406,803 discloses the use of alkane-1,2-diols in
lubricants
to improve fue! economy of an internal combustion engine.
U.S. Patent No. 4,512,903 disctoses amides prepared from mono or poly
hydroxy substituted aliphatic monocarboxytic acids and primary or secondary
amines which are useful as friction reducing agents.
3o Accordingly, it is an object of the present invention to provide a
composition
for reducing andlor preventing friction.
It is another object of the present invention to provide a method for reducing
friction in the operation of an internal combustion engine.
The instant invention is directed to carbamates prepared via condensation of
35 alkylamines and dialkylcarbonates andlor alkylene carbonates which have
been
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s found to be effective friction reducing additives for fuels, particularly
gasoline, fuel
additive concentrates, lubricants and lubricant additive concentrates, with
good high
temperature decomposing cleanliness.
In accordance with the invention, there is provided a lubricant composition
comprising a lubricating oil or grease prepared therefrom and a friction
reducing
io amount of a reaction product obtained by reacting
RXR'NHz
wherein X = CHZ, 0, S, or NH;
R= hydrogen, hydrocarbyl, alkenyl, or alkyl (C, to Cue);
R'= C, to C,, alkenyl or substituted alkenyl;
is and dialkylcarbonate andlor alkylene carbonate.
There is further provided a fuel composition comprising an internal
combustion engine fuel and a friction reducing amount of a product obtained by
reacting
RXR' NHZ
2o wherein X= CH2, 0, S, or NH;
R= hydrogen, hydrocarbyl, alkenyl, or alkyl (C, to Cso);
R'= C, to C4 alkenyl or substituted alkenyl;
and dialkylcarbonate andlor alkylene carbonate.
There is still further provided a method for reducing andlor preventing
friction
2s in the operation of an internal combustion engine which comprises fueling
said
engine with a liquid fuel composition comprising per 1000 barrels of fuel
between 25
to 250 pounds of a product obtained by reacting
RXR'NH2
wherein X= CH2, 0, S, or NH;
3o R= hydrogen, hydrocarbyl, alkenyl, or alkyl (C, to Coo);
R'= C, to Ca alkenyl or substituted alkenyl;
and dialkylcarbonate andlor alkylene carbonate.
Reaction products of dialkyicarbonates andlor alkylene carbonates and
alkylamines have been found to have excellent friction reduction properties
coupled
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s with excellent high temperature cleanliness and decomposition features
necessary
for use in high quality fuels and lubricants for internal combustion engines.
Suitable alkylamines include pure saturated or unsaturated monoamines
and/or diamines or mixtures of alkylamines derived from fatty acids, such as
coco,
oleyl or tallow.
io The alkylamines can also contain heteroatoms such as oxygen, sulfur or
nitrogen in their alkyl chains. The alkyl groups on the amines are long enough
to
confer friction reduction properties but not too tong to prevent the inherent
waxiness
of long chain paraffins. However, the waxiness may be minimized by introducing
a
site of unsaturation or a heteroatom into the alkyl chain.
~s Suitable diaikylcarbonates include dimethylcarbonate and diethylcarbonate.
Dimethyl carbonate is preferred.
The resulting alcohol byproduct may be removed by distillation. However,
keeping the alcohol in the mixture does improve the fluidity of the final
product.
Suitable alkylene carbonates include cyclic ethylene carbonate and
2o propylene carbonate. Propylene carbonate is preferred. There is no alcohol
byproduct when an alkylene carbonate is used as a reactant.
Hydrocarbon solvents or other inert solvents may be used in the reaction.
Included among useful solvents are benzene, toluene and xylenes. When solvent
is
used, the preferred solvent is a mixture of xylenes. In general, any
hydrocarbon
2s solvent can be used in which the reactants and products are soluble and
which can
be easily removed.
The condensation reaction with dialkylcarbonate generally proceeds as
follows:
RXR'NH2 + RZOCOOCR2 --~ RX'R'NHCOOR2 + R20H
3o wherein X= X' = CH2, O, S, NH; when X= NH, X' can be NCOOR2
R= hydrogen, hydrocarbyl, alkenyl, alkyl (C, to Cs~) optionally containing
aryl,
alkylaryl;
R'= C, to C, alkenyl or substituted alkenyl; and
RZ = C, to C4 alkyl.
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s The condensation reaction with alkyiene carbonate generally proceeds
as follows:
RXR'NH2 + (R3)OCOO(R4) -~ RX'R'NHCOO(R3)(R4)OH
wherein X= X' = CHZ, O, S, NH; when X= NH, X' can be NCOO(R3)(R°)OH
R= hydrogen, hydrocarbyi, alkenyl, alkyl (C, to Cso) optionally containing
aryl,
io alkylaryl.
R'= C, to C, atkenyl or substituted alkenyl;
R2 = C, to C, alkyl; and
(R3)(R4)= ethylenyl or methylethylenyl.
Generally the reaction temperature is in the range of from ambient to
165°C
is and preferably in the range of from ambient to 100°C. The reaction
time is
generally in the range of from 1 to 24 hours and preferably in the range of
from 2 to
12 hours.
It is preferred to use stoichiometric quantities of amines and
dialkyicarbonates andlor alkylene carbonates. However, excess of one or
another
2o reagent can be desirable. The generated alcohol, if present, is generally
left in the
final compound mixtures.
The amount of friction reducing additive in the lubricant composition may
range from 0.1 to 10% by weight of the total lubricant composition. Preferred
is from
0.1 to 2.0 wt.%.
2s In the lubricant additive concentrate the amount of friction reducing
additive
may range from 1.0% to 50.0% by weight of the total lubricant additive
concentrate.
Preferred is from 10°~ to 30% by weight.
The lubricant composition and/or the lubricant additive concentrate may
contain other materials normally present in additive packages including
dispersants,
3o detergents, antioxidants, antiwear and extreme pressure agents, viscosity
index
improvers; corrosion inhibitors, anti-rust additives, antifoam agents, pour
point
depressants, various markers, taggants, and any soiubilizing agents, such as
oils,
polymers, solvents, and the like. These materials impart their customary
properties
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s
s to the particular compositions and do not detract from the value of the
compositions
into which they are incorporated.
Suitable dispersants include polyalkylene succinimides, Mannish bases,
polyethers, polyalkylene amines, various esters, and the like.
Suitable detergents include metallic andlor non-metallic phenates, sulfonates,
io carboxyiates, and the like.
Suitable antioxidants include hindered phenols, aryiated amines, sulfurized
olefins, and the like.
Suitable viscosity index improvers include polymethacrylates, olefin
copolymers and the like.
1s Suitable antiwear and extreme pressure agents include zinc dialkyl
dithiophosphates, dithiocarbamates, thiodiazoles, and the like.
Generally the total amount of all such other materials will not exceed 10.0 to
30.0 wt.% in the lube compositions and 10.0 to 100.0% of the lube additive
concentrates.
2o Furthermore, the lubricants contemplated for use herein include both
mineral
and synthetic hydrocarbon oils of lubricating viscosity, mixtures of mineral
and
synthetic oils and greases prepared therefrom, and other solid lubricants. The
synthetic oils may include polyalphaolefins; polyalkylene glycols, such as
polypropylene glycol, polyethylene glycol, polybutylene glycol; esters, such
as di(2-
2s ethylhexyl)sebacate, dibutyi phthalate, neopentyl esters, such as
pentaerythritol
esters, trimethyl propane esters; polyisobutylenes; polyphenyls; ethers such
as
phenoxy phenylethers; fluorocarbons; siloxanes; silicones; silanes and
silicate
esters; hydrogenated mineral oils or mixtures thereof.
The present invention may also be used in fuels such as gasoline,
30 oxygenated gasolines, reformulated gasolines, gasohols, hydrocarbon fuels,
mixed
hydrocarbon and oxygenated fuels, jet turbine engine fuels and diesel fuels.
The
present invention may also be used in fuel additive concentrates.
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Fuel compositions can contain from 10 to 1,000 pounds of friction reducing
additive per 1,000 barrels of fuel or more preferably from 25 to 250 pounds
per
1,000 barrels of fuel.
In the fuel additive concentrate the amount of friction reducing additive may
range from 1.0% to 50.0% by weight of the total fuel additive concentrate.
Preferred
io is from 10% to 30% by weight.
Fuel and fuel additive concentrates may contain other materials normally
present in fuel additive packages including deposit control additives for
carburetors,
port fuel injectors, intake ports, intake valves, and combustion chambers;
carrier
fluids; anti-knock agents, such as tetraalkyl lead compounds, organomanganese
is compounds, lead scavengers, octane enhancing additives, and the like; dyes;
markers; taggants; cetane improvers, such as alkyl nitrates, alkyl peroxides,
and the
like; antioxidants, such as hindered phenols, aryiated amines, sulfurized
olefins, and
the like; rust inhibitors; demulsifiers; bacteriastatic agents; gum
inhibitors; anti-icing
agents; metal deactivators; exhaust valve anti-recession agents; spark
enhancing
2o additives; low temperature solubilizers; solvents necessary for low
temperature
performances or mixtures thereof.
Suitable demuisifiers include oxyalkylated alkylphenolic (formaldehyde)
resins, and polyoxyalkyiene glycols.
Suitable carrier fluids include mineral andlor synthetic oils, polyalkylenes,
25 sters, polyols, polyethers or mixtures thereof.
Suitable corrosion inhibitors include alkyl lactic succinate esters.
The fuel and fuel additive concentrates generally comprise an effective
amount of at least one detergent. The detergent is normally selected from the
group
consisting of polyalkyleneamines and Mannich base-type condensation products
of
so hydrocarbyl phenols, aldehydes and amines. Generally, these detergent
agents
reduce andlor prevent deposits which have a tendency to form in carburetors
and
fuel injection systems, thereby improving engine pertormance. Such detergent
agents also improve fuel economy and reduce internal combustion engine exhaust
emissions.
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s ~ The preferred polyalkyleneamine detergents are selected from the group
consisting of polymeric 1-amines, including polyisobutylene-amines. High
vinylic
content polyisobutylene-amines are most preferred. Suitable polyisobutylene-
amines are described in U.S. Patent Nos. 5,004,478 and 5,112,364, and DE
3942860. Preferred polyisobutylene-amines have an average molecular weight of
uo 500 to 3,000 or greater.
Such polyalkyleneamines are available from normal commercial sources or
may be prepared by the amination of high vinylic content polyolefins having an
average molecular weight of from 500 to 3000 or greater, using methods which
are
well known to those skilled in the art. Polyisobutylene amines are generally
is prepared by chlorination or hydroformylation of reactive polyisobutylene
and
subsequent amination with ammonia, hydrocarbyi amines, hydrocarbyl diamines,
hydrocarbyl polyamines, alkoxylated hydrocarbyf amines, or mixtures thereof.
Ammonia, ethylenediamine, diethylenetriamine, triethylene-tetramine,
tetraethylenepentamine, piperazines, hexamethylenediamine, hydroxyalkyl
2o ethylenediamines, hydroxyalkyl triethylenetetraamines, and the like can be
incorporated into the polyalkeneamines. Such amines can be prepared by the
chlorination or haiogenation of appropriate polymeric olefins, and
subsequently
converted into corresponding polyalkene derivatives using these or other known
methods of manufacture.
2s The amount of polyalkyleneamine in the fuel composition may be at least 10
to 200 pounds per 1,000 barrels of fuel and preferably at least 40 to 150
pounds per
1,000 barrels of fuel.
The amount of polyalkyleneamine in the fuel additive concentrate may be at
least 10 wt.%, preferably at least 20 wt.%, and most preferably in the range
of from
30 25 to 60 wt.%.
Alternatively, preferred detergent agents are the Mannich base condensation
products of hydrocarbyl phenols, aldehydes, and amines. The hydrocarbon-
substituted phenols are generally prepared by the alkylation of phenol or
phenolics
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s with hydrocarbyl groups having from 10 to 150 carbon atoms. For instance,
long
chain olefins or polymeric olefins such as propylene and polyisobutylene can
be
used in the phenol alkylation step. The substituted phenol is then reacted
with a
carbonyl source and an amine. Carbonyl sources include aldehydes, such as
formaldehyde, acetaldehyde, propanal, butanal, and 2-ethylhexanal. In
addition,
io aromatic aldehydes may be used to provide a carbonyl source. For instance,
benzaldehyde, tolualdehyde, vanillin, salicylaldehyde, and cinnamaidehyde may
be
used. Pofycarbonyl compounds, such as paraformaldehyde or glyoxat can also be
used in some aspects of the invention.
Amines useful in the preparation of the Mannish base condensation product
is include primary or secondary amines and amides. Fatty amines, hydroxyl-
containing amines, or polyamines, such as di-, tri-, tetra- and pentamines can
be
used in some aspects of the invention. For example, linear and cyclic Cz-Cs
alkylene di-, tri-, tetra- and pentamines, polyamines, and their substituted
polyfunctional derivatives can be used. Substituted derivatives, as used
herein,
2o refer to substitution with substituents such as halo, hydroxy, alkoxy,
vitro, thio,
carbalkoxy and alkythio substituents. Such Mannish base condensation products
are available from normal commercial sources. Suitable Mannish base
condensation products are described in U.S. Patent No. 5,169,410.
The amount of Mannish base condensation product in the fuel compo-sition
25 may be at least 10 to 200 pounds per 1,000 barrels of fuel and preferably
at least
40 to 150 pounds per 1,000 barrels of fuel.
The amount of Mannish base condensation product in the fuel additive
concentrate may be at least 10 wt.%, preferably at least 20 wt.%, and most
preferably in the range of from 25 to fi0 wt.%.
3o A concentrate utilizing the friction reducing additive of the present
invention
typically also comprises 15 to 80% solvent. A preferred composition range is
as
follows:
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9
s Component Wt.% Range
Carbamate 5 to 25
Detergent 20 to 60
Solvent
io Isopropanol 0 to 30
Xylene 15 to 50
Where the presently described invention is used as a gasoline additive, the
additive package may be added at any point after the gaoline has been refined,
i.e.
is the additive pacakge can be added at the refinery or in the distribution
system.
'The invention also includes a method for reducing andlor preventing friction
in the operation of an internal combustion engine. Additional possible
benefits
realized from the present invention include enhanced engine cleanliness,
enhanced
lubricity, enhanced corrosion protection, reduced fuel consumption, increased
power
2o benefits, and reduced wear. The method comprises delivering to the internal
combustion engine a fuel comprising gasoline and a friction reducing additive,
and
other materials normally present in additive packages, described above.
The following examples are illustrative of the present invention.
Example 1
2s One hundred ninety five grams (0.7 mole) of a fatty oleylamine (Armeen*OL,
commercially obtained from Akzo Chemicals, Inc:) and 70 ml. (0:7 mole) of
dimethylcarbonate were heated at 100°C for 2 hours under an inert
nitrogen
atmosphere. The methanol formed during the reaction was constantly removed by
distillation using a moisture trap. Two hundred three grams of a yellow liquid
was
30 obtained.
Example 2
One thousand nine hundred ninety five grams (7.5 moles) of a fatty
cocodiamine, N-coco-1,3-propanediamine (Duomeen*C, commercially obtained from
Akzo Chemicals, Inc.) and 1350 grams. (15.0 moles) of dimethylcarbonate were
ss heated at reflex for 3.5 hours. Three thousand two hundred ninety two grams
of a
clear slightly brownish yellow liquid containing 14 wt.% methanol, was
obtained.
* Trade-mark
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to
s Example 3
Four hundred grams (1.5 moles) of a fatty cocodiamine, N-coco-1,3-
propanediamine (Duomeen*C, commercially obtained from Akzo Chemicals, Inc.)
and 323.0 grams (3.15 moles) of propylenecarbonate (Texaca~ PC, commercially
Zo obtained from Texaco Chemical Company) in 145 grams of xylenes as solvent
were
heated at 100°C for 4 hours then 165°C for an extra hour. Seven
hundred twenty
grams of a clear brownish liquid was obtained.
The friction reducing properties of the products in the examples were
measured using LVFA (Low Velocity Friction Apparatus) test and/or a Buick 3.8L
is Fired Engine test. The additives were dissolved at 1.00 or 0.50 or 0.25
wt.% into a
fully formulated 5W-30 mineral engine oil used as reference.
(n the LVFA test, the coefl'acients of friction of the reference oil and the
oils
containing the products of this invention were measured at 32, 38, 48 and 58
psi
over a range of sliding speeds (5-30 ftlmin.) at both room temperature and
250°F
20 and averaged. The percent changes in the coefficients of friction of the
test oils
relative to the reference oil are reported in Table 1 below. Also reported and
used
as reference are the results of a commercially available friction modifier,
glycerol
monooleafe (GMO). The larger the percent reduction in the coefficient of
friction,
the effectiveness of the additive is increased. The N-alkylmethylcarbamate of
2s Example 1 is superior to GMO in friction reduction.
Table 1
Change in the Coefficients of Friction
Example Treat Rate Coefficients of Friction % Reduction
so wt.% Static Dynamic
1 0.5 15.5 12.0
GMO 0.5 7.0 4.0
A 3.8L Fired Engine test measures brake specific fuel consumption (BSFC)
ss for each sample and the results are compared to those of the unadditized
engine oil
used as reference.
* Trade-mark
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s The experiments are generally additive spike additions to the lubricating
oil of
the engine run at a temperature of 275°F (i 36°C).
The percent reduction in fuel consumption results reported in Table 2 below
are percent improvement over the reference oil. The larger the percent
reduction in
BSFC; the more effective is the additive. Here also, GMO (glycerol monooleate)
io results were used as reference for comparative reasons.
Table 2
Reduction in Fue! Consumption
is Exam le Treat Rate % Reduction in Fuel Consumption
Vvt. % 275° F
1 1 4.2
2 1 4.8
20 3 1 4.1
GMO 1 2.0
*No response
2s As can be seen from the low velocity friction apparatus test results and
8lso
from the 3.8L Fired Engine test results; the products of this invention show
exceptional friction reduction properties leading to enhanced fuel economy and
better performance than the commercially available friction modifier additive,
glycerol monooleate.
so The products of the examples were also evaluated with respect to
cleanliness
during thermal decomposition using TGA (Thermogravimetric Analysis) and the
results are compared to a commercially available friction modifier, glycerol
monooleate (GMO) as shown in Table 3 below. Thermo- gravimetric analysis was
performed by heating a small sample at 20°Clmin. with an air flow of
100 mllmin.
3s using a Thermogravimetric Analyzer. The percent residue remaining at
425°C was
recorded; little or no residue is desirable.
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12
Fable 3
Cleanliness
Example Thermoaravimetric Analysis
to °lo Residue fo? 424°C
1 8.5
2 5.0
3 3.3
is GMO 25.0
As can be seen from the thermogravimetric analysis results in Table 3, the
products of this invention show exceptionally higher cleanliness than the
commercially available friction modifier, GMO. The N-afkylmethylcarbamates of
2o Examples 1 and 2 and The N-alkyl(2-hydroxy propyl)carbamate of Example 3
are
superior to GMO in cleanliness.
The t~esults of the LVFA and TGA shown in the above Tables show the
superiority of the products of the present invention over the glycerol
monooieate as
friction reducers as well as in the cleanliness of decomposition. 1t is also
believed
2s that the additional groups on the amides such as hydroxyl, amino, imino and
atkoxy
contributes to better surface activity in synergy with the amide function.
Example 4
Using the reaction product of Example 2, the following fuel. additive
concentrate formulations are prepared.
30 ,
formulation ~ A B C D E F
Component (Wt.°lo Range)
Example 2 reaction product 15.0 14.88 22.7 19.46 29.7 10.0
3s Deterq_ent
Mannich-base condensation 30.12 47.3 40.3 45.0
product (Ethyl*4961M)
Polyisobutylene amine 30.0 40.54
(Pluradyne*AP-92M)
~o
Solvent
tsopropanol 18.33 9 8.33 10.0 13.3 10.0 8.0
Xylene 36.67 36.67 20.0 26:67 20.0 37.0
* Trade-mark
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Example 5
Using the reaction product of Example 3, the following fuel additive
concentrate formulations are prepared:
Formulation A B C D E F
Component (Wt.% Range)
to Example 3 reaction product i 5.0 14.88 22.7 19.46 29.7 10.0
Detergent
Mannish-base condensation 30.12 47.3 40.3 45.0
product (Ethyl 4961 M)
is Polyisobutylene amine 30.0 40.54
(Pluradyne AP-92M)
Solvent
Isopropanol 18.33 18.33 10.0 13.3 10.0 8.0
2o Xylene 36.67 36.67 20.0 26.67 20.0 37.0
The invention having now been fully described, it should be understood that it
may be embodied in other specific forms or variations without departing from
its
spirit or essential characteristics. Accordingly, the embodiments described
above
25 are to be considered in all respects as illustrative and not restrictive,
the scope of
the invention being indicated by the appended claims rather than by the
foregoing
description, and all changes which come within the meaning and range of
equivalency of the claims are intended to be embraced therein.
