COMPOUNDS CONTAINING AMIDE LINKAGES FROM MONO-AND POLYCARBOXYLIC ACIDS IN THE SAME MOLECULE AND LUBRICANTS AND FUELS CONTAINING SAME

COMPOSE DERIVES D'ACIDES MONO- ET POLYCARBOXYLIQUES RENFERMANT DES LIAISON AMIDES DANS LA MEME MOLECULE; LUBRIFIANTS ET COMBUSTIBLES QUI EN CONTIENNENT

English Abstract

COMPOUNDS CONTAINING AMIDE LINKAGES FROM MONO- AND
POLYCARBOXYLIC ACIDS IN THE SAME MOLECULE AND LUBRICANTS
AND FUELS CONTAINING SAME
ABSTRACT OF THE DISCLOSURE
Lubricant and fuel additives having excellent dispersant
properties have amide linkages, in the same molecule, derived from
mono- and polycarboxylic acids. The additives are produced by
reacting (1) at least one fatty monocarboxylic acid, (2) at least
one alkenyl- or alkylsuccinic acid and anhydride and (3) at least
one polyamine.

Claims

--9--
CLAIMS
l. A product formed by reacting (1) at least one fatty
monocarboxylic acid containing 10 to 20 carbon atoms, (2) at least
one alkenyl- or alkylsuccinic acid or acid anhydride thereof, where
the alkenyl or alkyl group is derived from a mixture of C12 to
C26 olefins and (3) at least one polyamine of the formula
<IMG>
wherein R is a hydrocarbyl group containing 1 to 5 carbon atoms,
R1 is a C1 to C5 alkylene group and x is 1 to 9.
2. The product of claim 1 wherein the fatty monocarboxylic
acid is selected from capric, lauric, myristic, palmitic, stearic,
arachidic, oleic, linoleic, linolenic, eleostearic, ricinoleic acids
and mixtures thereof.
3. The product of claim 1 wherein
the polyamine is selected from triethylenetetramine,
tetraethylenepentamine, pentaethylenedexamine, nonethylenedecamine
and the methylene, propylene, butylene and amylene counterparts
thereof.
4. The product of any one of claims 1-3 wherein
the alkenyl- or alkylsuccinic acid or anhydride has the formula
<IMG>
where R is an alkenyl or alkyl group derived from 3 mixture of C18
to C24 monomers.

--10--
5. The product of any one of claims 1-3 wherein
the fatty monocarboxylic acid comprises between about 30 and about
90 percent by weight of the total amount of monocarboxylic and
alkenyl-, or alkylsuccinic acids or acid anhydride reacted.
6. The product of any one of claims 1-3 wherein
the quantity of polyamine selected is one wherein at least 40% by
weight of the available amino groups therein are reacted with the
acids.
7. The product of any one of claims 1-3 wherein
the reaction is conducted by reacting one of acids (l) and (2) with
amine (3) at a temperature of from 100° to 175°C and then reactingthis product with the other acid at the same temperature.
8. The product of any one of claims 1-3 wherein
the reaction is conducted by reacting amine (3) with a mixture of
acids (1) and (2) at a temperature of from 100°C to 175°C.
9. A process for making a dispersant for fuel and
lubricating compositions comprising reacting (1) at least one fatty
monocarboxylic acid containing 10 to 20 carbon atoms, (2) at least
one alkenyl- or alkylsuccinic acid or acid anhydride, where the
alkenyl or alkyl group is derived from a mixture of C12 to C26
olefins and (3) at least one polyamine of the formula
<IMG>
wherein R is a hydrocarbyl group containing 1 to 5 carbon atoms,
R1 is a C1 to C5 alkylene group and x is 1 to 9.
10. The process of claim 9 wherein the fatty
monocarboxylic acid is selected from the group consisting of capric
lauric, myristic, palmitic, stearic, arachidic, oleic, linoleic,
linolenic, eleostearic and ricinoleic acids and mixtures thereof.

--11--
11. The process of claim 9 wherein the
polyamine is selected from the group consisting of
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
nonethylenedecamine and the methylene, propylene, butylene and
amylene counterparts thereof.
12. The process of any one of claims 9, 10 and 11 wherein
the alkenyl- or alkylsuccinic acid or anhydride has the formula
<IMG>
wherein R is an alkenyl or alkyl group derived from a mixture of
C18 to C24 monomers-
13. The process of any one of claims 9-11 wherein the
fatty monocarboxylic acid comprises between about 30 and about 90
percent by weight of the total amount of monocarboxylic and
alkenyl-, or alkylsuccinic acids or acid anhydride reacted.
14. The process of any one of claims 9-11 wherein at least
40% by weight of the polyamine available amino groups therein are
reacted with the acids.
15. The process of any one of claims 9-11 wherein the
reaction is conducted by reacting one of acids (1) and (2) with
amine (3) at a temperature of from 100° to 175°C and then reactingthis product with the other acid at the same temperature.
16. The process of any one of claims 9-11 wherein the
reaction is conducted by reacting amine (3) with a mixture of acids
(1) and (2) at a temperature of from 100° to 175°C.

--12--
17. A fuel conoposition comprising a major proportion of a
liquid fuel and a dispersant amount of the product of claim 1.
18. The fuel composition of claim 17 wherein the
dispersant constitutes 0.00001% to 0.1% by weight of the composition.
19. A lubricant composition comprising a major proportion
of a liquid lubricant and a dispersant amount of the product of
claim 1.
20. The lubricant composition of claim 19 wherein the
dispersant constitutes 1.0% to 5.0% by weight of the composition.

Description

5~
F-3289
COMPOUNDS CONTAINING AMIDE LINKAGES FROM MONO- AND
POLYCARBOXYLIC ACIDS IN THE SAME MOLECULE AND LUBRICANTS
AND FUELS CONTAINING SAME
The invention relates to dispersant additives and to fuel
and lubricant compositions containing them. In particular, it
relates to certain amides made from polyamines, monocarboxylic acid
and polycarboxylic acid.
It is known that in the normal use of organic industrial
fluids, such as lubricating oils, transmission fluids, bearing
lubricants, powzr transmitting fluids and the like, oxidizing
conditions are encountered wnich may result in the formation of
sludge, lacquers, corrosive acids and the like~ These products are
undesirable in that they produce oxidation residues or heavy
contaminants which may cause normal breakdown of the fluid, leading
eventually to severe damage to the parts of the equipment being
lubricated.
In the lubrication of modern engines, oil compositions must
be able to prevent acids, sludge and other solid contaminants from
remaining near the moving metal parts. Poor piston travel and
excessive eng;ne bearing corrosion may result unless the oil can
prevent sludge and oxidation products from depositing in the
engine. Bearing corrosion is another serious problem in gasoline
engines which operate at an oil temperature of about 149C (300F)
or higher.
The most desirable way of decreasing the effect of these
problems is to add to the base organic fluid a detergent or
dispersant additive capable of dispersing the solid particles to
prevent them from interfering with the normal operation of the
equlpment, thereby leaving the metal surfaces relatively clean.
Today, with modern equipment operating under increasingly strenuous

F-32~9 --2--
conditions, it is desirable to develop new detergents which have
improved dispersant properties, which are soluble in the fluid
medium to which they are added, and which are themselves stable
therein.
U.S. Patent 3,714,045 discloses lubricant compositions
containing lubricants and a polyimide produced by reacting (1) a
heteropolymer produced by reacting an olefin with maleic anhydride
in the presence of a free-radical initiator with (2) a primary
arylamine.
uOs. Patent 3,936,480 discloses the reaction of a
polyalkylenesuccinic acid anhydride with diphenylolpropane of the
formula
( ~ ) 2
and tetraethylenepentamine, pyridine or triethylenetetramine. It
should be noted, however, that in all cases wherein diphenylolpropane
is reacted, a catalyst is used. This is an absolute necessity when
a phenolic OH is present, because there will be no reaction with the
anhydride without it.
U.S. Patent 3,868,330 discloses a lubrlcant or fuel composition
containing an additive amount of at least one oil-soluble high
molecular weight compound made by chlorinating
(1) a mixture of a C5U monocarboxylic acid and a low
molecular weight polycarboxylic acid, e.g., succinic acid;
or
(2) a mixture of a C50 ethyleneically unsaturated
aliphatic hydrocarbon, a low molecular weight
monocarboxcylic acid and a low mol~cular weight
polycarboxylic acid.
This invention provides a reaction product prepared by
reacting (1) at least one fatty monocarboxylic acid containing 10 to
20 carbon atoms, (2) at least one alkenyl- or alkylsuccinic acid or
.~ ' .

F-3289 __3__
anhydride, where the alkenyl group is derived from a mixture of
C12 to C26, preferably C18 to C24, olefins and (3) at least
one polyamine of the formula
RNH[RlNt ~ H
wherein R is a hydrocarbyl group containing 1 to 5 carbon atoms,
Rl is a Cl to C5 alkylene group and x is 1 to 9.
This invention also provides a process for making a
dispersant for fuel and lubricating compositions comprising reacting
(1) at least one fatty monocarboxylic acid containing 10 to 20
carbon atoms, (2) at least one alkenyl- or alkylsuccinic acid or
acid anhydride where the alkenyl or alkyl group is derived from a
mixture of C12 to C26 olefins and (3) at least one polyamine of
the formula
RNH[RlNH ~ H
wherein R and Rl have the definitions given above.
The present invention ~urther provides a lubricant or
liquid fuel comprising a major proportion of a lubricant or liquid
~uel and a dispersant amount of a product obtained by the process
described hereinabove.
The preferred method of preparing the reaction products of
this invention involves reacting one of the two types of acids with
the amine at from about 100C to about 175C, preferably about 150C
to about 175C, then reacting this product with the other acid at -
the same temperature.
The two types of acids will be used in such amounts that
one type will supply from about ~0% to about 90% by weight of the
required amount and the other type will supply the complementary
amount. The quantity of polyamine will be chosen such that the
acids react therewith to form amide or imide groups with at least
40% by weight of the available amino groups. Preferably from about
30% to about 60% of the amino groups are left unreacted, but an
, : .

F-328~ 4 _
effective dispersant is obtained when 60~ of the amino groups is
reacted with the acid mixture.
Another method that can be used to form the product
involves reacting the amine with a mixture of the acids. The same
temperature mentioned for the preferred method may be used for both
acid-amine reactions. Further, the final product is made by using
the same relative proportions of acid mentioned above, and the
percentage of reacted amino groups in a given product will be the
same.
The useful fatty monocarboxylic acids have the formula
R - COCH
where R is a hydrocarbyl group containing 10 to 20 carbon atoms.
Among the saturated members covered by the formula are capric,
lauric, myristic, palmitic, stearic and arachidic and tall oil fatty
acids. The unsaturated members include oleic, linoleic, linolenic,
eleostearic and ricinoleic acids.
The preferred polycarboxylic acids and anhydrides
contemplated have the formula
O O
1~ 1!
R - CH - C - OH R - CH - C
¦ or¦ /0
CH2 - C - OH CH2 ICj
O O
where R is an alkenyl or alkyl group derived from a mixture of C18
to C24 monomers. Polyamines include triethylene-
tetramine, te-traethylenepentamine, pentaethylenehexamine, etc. to
nonaethylenedecamine, and the methylene, propylene, butylene and
amylene counterparts.

~ R~
F-3289 --5--
The additive compositions of the present invention impart
valuable properties, as hereinbefore indicated, to liquid
hydrocarbon combustion fuels, including the distillate fuels, i.e.,
gasolines and fuel oils. The fuel oils that may be improved in
accordance with the present invention are hydrocarbon fractions
having an initial boiling point of at least about 38C (100f) and
an end-boiling point no higher than about 399 (750F), and boiling
substantially continuously throughout their distillation range.
Such fuel oils are generally known as distillate fuel oils. It is
to be understood, however, that this term is not restricted to
straight run distillate Fractions. The distillate fuel oils can be
straight run distillate fuel oils, catalytically or thermally
cracked (including hydrocracked) distillate fuel oils, or mixtures
of straight run distillate fuel oils, naphthas and the like, with
cracked distillate stocks. Moreover, such fuel oils can be treated
in accordance with well-known commercial methods, such as, acid or
caustic treatment, hydrogenation, solvent refining, clay treatment
etc.
The distillate fuel oils are characterized by their
relatively low viscosities, pour points, and the like. The
principal property which characterizes the contemplated
hydrocarbons, however, is the distillation range. As mentioned
hereinbefore, this range will lie between about 38C (100F) and
about 399C (750F). Obviously, the distillation range of each
individual fuel oil will cover a narrower boiling range falling,
nevertheless, within the above-specified limits. Likewise, each
fuel oil will ooil substantially continuously throughout its
distillation range.
Contemplated among the fuel oils are Nos. 1, 2 and 3 fuel
oils used for heating and as diesel fuel oils, and the jet
combustion fuels. The domestic fuel oils generally conform to the
specifications as set forth in A.S.T.M. Specifications D396-48T.
Specifications for diesel fuels are defined in A.S.T.M.
Specification D975-48T. Typical jet fuels are defined in Military
Speci~ication MIL-F-5624B.

LF~ 8
F-3289 --6--
The gasolines that are improved by the additive
compositions for this invention are mixtures of hydrocarbons having
an initial boiling point falling between about 24C (75F) and about
57C (135F) and an end-boiling point falling between about 121C
(25ûF) and about 232C (450F). As is well known in the art, motor
gasoline can be straight run gasoline or, as is more usual, it can
be a blend of two or more cuts of materials including straight run
stock, catalytic or thermal refo~nate, cracked stock, alkylated
natural gasoline, and aromatic hydrocarbons. The concentration of
additive in the fuel will range from about 0.00001% to about 0.1~ by
weight of the composition.
The additive is effective in lubricant compositions for the
purposes disclosed in ranges from about û.1% to about lû.0% by
weight of the total lubricant composition. Preferred is from about
1.0% to 5.0~. In general, the additives of this invention may also
be used in combination with other additive systems in conventional
amounts for their known purpose. The use of additive concentrations
of borated alcohols in premium quality automotive and industrial
lubricants further improves upon such fluids' Fuel economy
characteristics. The non-metallic compositions described herein are
useful at said moderate concentrations and do not contain any
potentially undesirable phosphorus, corrosive sulfur or metallic
salts.
The lubricants contemplated for use herein include both
mineral oil and synthetic hydrocarbon or hydrocarboxy oils of
lubricating viscosity, mixtures of mineral oils and such synthetic
oils, and greases prepared therefrom. The synthetic hydrocarbon
oils include long chain alkanes such as cetanes, and olefin polymers
such as trimers and tetramers of octene and decene. Such synthetic
hydrocarbon oils can be mixed with other synthetic oils, incloding
(1) ester oils such as pentaerythritol esters of monocarboxylic
acids having 2 to 20 carbon atoms, (2) polyglycol ethers, and (3)
polyacetals. Especially useful among the synthetic esters are those
made from polycarboxylic acids and monohydric alcohols. More

~d ~
F-3289 --7--
preferred are the ester fluids made from pentaerythritol, and an
alipnatic monocarboxylic acid containing from 1 to 20 carbon atoms,
or mixtures of such acids.
The following example is offered as a specific illustration
of the invention.
EXAMPLE
A mixture of 1~99 (1.0 mole) of tetraethylenepentamine and
712.5g (2.5 moles) of tall oil fatty acids was heated to about 175C
and was stirred over a three hour period, evolving 45.0 g (2.5
moles) of water. A typical tall oil fatty acid contains about
45-50% oleic acid, 45-50% linoleic acid and 1-6% rosin acids.
Subsequently, 106 grams (0.25 mole) of mixed C18 to C2~
alkenylsuccinic anhydride derived from ethylene polymerization were
added and the mixture was stirred for one hour at 175C under
reduced pressure to aid in the removal of water. The final product
was obtained by filtration.
The deposit-forming tendencies of a fuel were determined in
an 8-hour engine test. This accelerated test, when run on fuels
that contain no detergents, produces an amount of deposit equivalent
to the amount observed in 4,000 miles of operation in field tests on
taxicab fleets. In accomplishing the test1 a Ford 4.9 liter (300
C.I.D.) engine was equipped with notched rings to increase the
amount of blowby and with a glass throttle body section. The engine
was operated for 8 hours, using the fuel under test, at alternate
idling and running cycles. In the idle cycle the engine was run for
5 minutes at idling speed of 400 rpm with no load. Then for 1
minute the engine was run at a speed of 2,500 rpm under a load of 30
BPH and a manifold pressure of 31.7 kPa (9.4 in. of mercury).
During the running cycle the blowby and part of the exhaust were
releàsed into the carburetor air intake during the idling cycle.
After 8 hours of operation at alternate run and idle, the carburetor
was examined and rated for amount of deposit in the throttle
throat. The fuel used was a gasoline comprising 40% catalytically
cracked component, 40% catalytically reformed component and 20%

F-3289 --8--
alkylate, the overall mixture having a boiling range of about
35-210C. The results are shown in the following table.
TABLE
Ford 4.9 Liter (300 C.I.D.) Carburetor Cleanliness Test
__ _
Conc. gm/1000 liters % Reduction
Composition (Lbs/1000 Bbls.)In Deposits
Base Fuel 0 0 0
Base Fuel Plus
Example 1 Product 7.1 (2.5) 60
Base Fuel Plus
Example 1 Product 14.3 (5.0) 85