Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
Fuel Additives For Use In Alcohol-Fuels
BACKGROUND OF THE INVENTION
The present invention relates to fuel additive concentrate, the fuel
additive concentrate in an alcohol fuel and the method for fueling an internal
combustion engine, providing improved fuel economy and retention of fuel
economy, deposit control, oxidation control, and wear and friction reduction.
Governments around the world are implementing the use of
nonhydrocarbonaceous fuels for economic and environmental reasons.
Oxygenates such as ethanol, butanol, isopropanol, methanol, methyl tert butyl
ether (MTBE) and ethyl tert butyl ether (ETBE) in particular are gaining
ground as alcohol and ether fuels of choice as they present renewable and/or
environmentally friendly alternatives to petroleum based fuels such as
gasoline
or diesel fuel. Additionally, fuels made from alcohol feedstocks benefit the
agricultural sector and therefore, have the backing of political and pricing
support. These factors in combination with rises in crude oil, desire for
energy
independence, and fears of global warming explain the recent growth in the
alcohol fuel market. Brazil has a long history of using fuel alcohol,
particularly
ethanol.
Alcohol fuels can have unique effects on engine hardware and lubricant
resulting in the tendency for increased engine deposits formation, accelerated
lubricant oxidation, increased wear of vital engine components, and a loss of
fuel economy. Some issues have been addressed through the development of
new vehicle technology, while other issues will require new inventive
additives
technology.
The present invention, therefore, solves the problems of associated with
alcohol fuels tendencies for engine deposits formation, lubricant oxidation,
engine wear and a loss of fuel economy by providing fuel additives to the
ethanol-gasoline blends that prevent engine deposits, slows lubricant
oxidation,
prevent wear and improve fuel economy.
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SUMMARY OF THE INVENTION
The present invention provides a fuel additive concentrate comprising:
a. detergent;
b. antioxidant; and
c. a friction modifier selected from the group consisting of an
alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture
thereof
wherein the detergent is soluble in a nonhydrocarbonaceous fuel.
The present invention further provides for a fuel composition
comprising:
a. a fuel which is a liquid at room temperature; and
b. additive
wherein the additive is selected from the group consisting of a detergent;
antioxidant; friction modifier selected from the group consisting of an alkoxy-
lated fatty amine, a fatty acid or derivative thereof, and mixture thereof;
and
mixtures thereof
wherein the detergent is soluble in a nonhydrocarbonaceous fuel.
The present invention further provides a method for fueling an internal
combustion engine, comprising:
A. supplying to an internal combustion engine:
i. a fuel which is a liquid at room temperature; and
ii. additive
wherein the additive is selected from the group consisting of a detergent;
antioxidant; friction modifier selected from the group consisting of an alkoxy-
lated fatty amine, a fatty acid or derivative thereof, and mixture thereof;
and
mixtures thereof
wherein the detergent is soluble in a nonhydrocarbonaceous fuel.
The present invention further provides for a use of the fuel composition
or fuel additive concentrate in an internal combustion engine providing at
least
one of the following: fuel system deposit control, injector deposit control,
intake valve deposit control, combustion chamber deposit control, wear
control,
improved fuel economy, and emission reduction (C02, NOx, or other gases).
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DETAILED DESCRIPTION OF THE INVENTION
Various preferred features and embodiments will be described below by
way of non-limiting illustration.
Field of the Invention
This invention involves fuel additive concentrate that includes: a
detergent, antioxidant, and a friction modifier selected the group consisting
of
an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture
thereof; wherein the detergent is soluble in a nonhydrocarbonaceous fuel.
The invention further involves a fuel composition that includes a fuel,
which is a liquid at room temperature, and an additive wherein the additive is
selected from the group consisting of a detergent; antioxidant; friction
modifier
selected from the group consisting of an alkoxylated fatty amine, a fatty acid
or
derivative thereof, and mixture thereof; and mixtures thereof; wherein the
detergent is soluble in a nonhydrocarbonaceous fuel.
The invention further involves a method of operating an internal
combustion engine comprising supplying to the internal combustion engine a
fuel which is a liquid at room temperature, and an additive wherein the
additive
is selected from the group consisting of a detergent; antioxidant; friction
modifier selected from the group consisting of an alkoxylated fatty amine, a
fatty acid or derivative thereof, and mixture thereof; and mixtures thereof;
wherein the detergent is soluble in a nonhydrocarbonaceous fuel.
The fuel additive concentrates, fuel compositions and methods of the
present invention promote engine cleanliness and fuel economy, while
controlling lubricant oxidation, which enables optimal engine operation.
Fuel
The present invention can comprise a fuel which is a liquid at room
temperature and is useful in fueling an engine. The fuel is normally a liquid
at
ambient conditions e.g., room temperature (20 to 30 C). The fuel is a
nonhydrocarbonaceous fuel. A nonhydrocarbonaceous fuel is a fuel obtained
from processes other than fuel streams obtained through the refining of fossil
fuels. The nonhydrocarbonaceous fuel can be obtained from fermentation
processes using bio-feed stocks, such as, corn, cellulose; sugar cane; or
other
agricultural or natural plant sources. The nonhydrocarbonaceous fuel can be
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obtained synthetically from hydrocarbonaceous or nonhydrocarbonaceous
ingredients. The nonhydrocarbonaceous fuel can be an oxygen containing
composition, often referred to as a oxygenate, which can include alcohols,
ethers, ketones, esters of a carboxylic acid, nitroalkanes, and mixtures
thereof.
The nonhydrocarbonaceous fuel can include, for example, methanol, ethanol,
propanol, butanol, methyl t-butyl ether, ethyl t-butyl ether, methyl ethyl
ketone,
transesterified oils and/or fats from plants and animals such as rapeseed
methyl
ester and soybean methyl ester, and nitromethane. In several embodiments of
this invention, the fuel can have a water content on a weight basis that is
about
10 percent by weight, or about 7 percent by weight, or about 5 percent by
weight, or about 3 percent by weight, or about 1 percent by weight, or less
than
1 percent by weight or 0 percent by weight. In another embodiment, the fuel
can be alcohol fuel, such as, punctilious alcohol or anhydrous alcohol or
hydrous alcohol, such as, A1Coo1TM. In another embodiment of the invention,
the fuel can be denatured ethanol (that is a blend of ethanol with a
denaturant).
The alcohol fuel can be denatured ethanol as defined by ASTM specification
D4806. In several embodiments of this invention, the denatured ethanol can
have a denaturant content on a weight basis that is about 10 percent by
weight,
or about 7 percent by weight, or about 5 percent by weight, or about 3 percent
by weight, or about 1 percent by weight, or less than 1 percent by weight or 0
percent by weight. In several embodiments the denaturant can be
hydrocarbonaceous or nonhydrocarbonaceous. In one embodiment, the
hydrocarbonaceous denaturant can be natural gasoline, refined gasoline,
kerosene, diesel fuel, or benzene. The hydrocarbonaceous denaturant can be a
petroleum distillate to include a gasoline as defined by ASTM specification
D4814 or a diesel fuel as defined by ASTM specification D975. In another
embodiment the nonhydrocarbonaceous denaturant can be diethyl phthalate,
isopropanol, phenylethyl alcohol, musk ketone, menthol, or benzyl salicylate.
In several embodiments of this invention, the fuel can have a sulfur
content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm
or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. In another
embodiment, the fuel can have a sulfur content on a weight basis of 1 to 100
ppm. In one embodiment, the fuel contains 0 ppm to 1000 ppm, or 0 to 500
ppm, or 0 to 100 ppm, or 0 to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to
5
ppm of alkali metals, alkaline earth metals, transition metals or mixtures
thereof. In another embodiment, the fuel contains 1 to 10 ppm by weight of
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alkali metals, alkaline earth metals, transition metals or mixtures thereof.
It is
well known in the art that a fuel containing alkali metals, alkaline earth
metals,
transition metals or mixtures thereof have a greater tendency to form deposits
and therefore foul or plug injectors. The fuel of the invention can be present
in
a fuel composition in a major amount that is generally greater than 50 percent
by weight, and in other embodiments is present at greater than 90 percent by
weight, greater than 95 percent by weight, greater than 99.5 percent by
weight,
or greater than 99.8 percent by weight.
Detergent
The detergent of the present invention, which is soluble in a
nonhydrocarbonaceous fuel can include polyetheramines, Mannich,
succinimides, polyisobutylene amines, glyoxylates, and mixtures thereof.
Polyetheramines of present invention can include compounds having
two or more consecutive ether groups and at least one primary, secondary or
tertiary amine group where the amine nitrogen has some basicity. The
polyetheramines of this invention can include poly(oxyalkylene) amines having
a sufficient number of repeating oxyalkylene units to render the
poly(oxyalkylene)amine soluble in a normally liquid fuel, such as, in
hydrocarbons boiling in a gasoline or diesel fuel range and blends of
hydrocarbon fuel with non-hydrocarbon fuel. Generally,
poly(oxyalkylene)amines having at least about 5 oxyalkylene units are suitable
for use in the present invention. Poly(oxyalkylene)amines can include:
hydrocarbylpoly(oxyalkylene)amines,
hydrocarbylpoly(oxyalkylene)polyamines, hydropoly(oxyalkylene)amines,
hydropoly(oxyalkylene)polyamines, and derivatives of polyhydric alcohols
having at least two poly(oxyalkylene)amine and/or
poly(oxyalkylene)polyamine chains on the molecule of the derivative. In one
embodiment, the poly(oxyalkylene)amine for use in the invention is
represented by the formula RO(AO)mRINR2R3 (I) wherein R is a hydrocarbyl
group of 1 to 50 carbon atoms, or about 8 to about 30 carbon atoms; A is an
alkylene group having 2 to 18 carbon atoms and preferably 2 to 6 carbon atoms;
m is a number from 1 to about 50; Rl is an alkylene group having 2 to 18
carbon atoms or preferably 2 to 6 carbon atoms; and R2 and R3 are
independently hydrogen, a hydrocarbyl group or -[R4N(R5)]nR6 wherein R4 is
an alkylene group having 2 to 6 carbon atoms, R5 and R6 are independently
hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.
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In another embodiment, the poly(oxyalkylene)amine of the present
invention can be represented by the formula:
RO[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (II) wherein R is an aliphatic
group or alkyl-substituted phenyl group of about 8 to about 30 carbon atoms;
and m is a number from about 12 to about 30. In yet another embodiment, the
poly(oxyalkylene)amine of the present invention can be represented by the
formula: CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O-
[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (III) wherein m is a number from
about 16 to about 28. Poly(oxyalkylene)amines of the present invention can
have a molecular weight in the range from about 300 to about 5,000.
The polyetheramines of the present invention can be prepared by
initially condensing an alcohol or alkylphenol with an alkylene oxide, mixture
of alkylene oxides or with several alkylene oxides in sequential fashion in a
1:1-50 mole ratio of hydric compound to alkylene oxide to form a polyether
intermediate. U.S. Patent Nos. 5,112,364 and 5,264,006 provide reaction
conditions for preparing a polyether intermediate.
The alcohols can be monohydric or polyhydric, linear or branched,
saturated or unsaturated and having 1 to 50 carbon atoms, or from 8 to 30
carbon atoms, or from 10 to 16 carbon atoms. Branched alcohols of the present
invention can include Guerbet alcohols, as described in U.S. Patent No.
5,264,006, which generally contain between 12 and 40 carbon atoms and can be
represented by the formula RCH(CH2CH2R)CH2OH (IV) where R is a
hydrocarbyl group. In one embodiment, the alkyl group of the alkylphenols can
be 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10 to 20 carbon atoms.
In one embodiment, the alkylene oxides include 1,2-epoxyalkanes
having 2 to about 18 carbon atoms, or 2 to about 6 carbon atoms. In yet
another embodiment, the alkylene oxides can be ethylene oxide, propylene
oxide and butylene oxide. Especially useful is propylene oxide, butylene
oxide,
or a mixture thereof. The number of alkylene oxide units in the polyether
intermediate can be 1-50, or 12-30, or 16-28.
The polyether intermediates can be converted to polyetheramines by
several methods. The polyether intermediate can be converted to a
polyetheramine by a reductive amination with ammonia, a primary amine or a
polyamine as described in U.S. Patent Nos. 5,112,364 and 5,752,991. In one
embodiment, the polyether intermediate can be converted to a polyetheramine
via an addition reaction of the polyether to acrylonitrile to form a nitrile
which
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is then hydrogenated to form the polyetheramine. U.S. Patent No. 5,264,006
provides reaction conditions for the cyanoethylation of the polyether with
acrylonitrile and the subsequent hydrogenation to form the polyetheramine. In
yet another embodiment, the polyether intermediate or poly(oxyalkylene)
alcohol is converted to the corresponding poly(oxyalkylene) chloride via a
suitable chlorinating agent followed by displacement of chlorine with ammonia,
a primary or secondary amine, or a polyamine as described in U.S. Patent No.
4,247,301.
The detergent of the present invention can be a Mannich detergent,
sometimes referred to as a Mannich base detergent. Mannich detergent is a
reaction product of a hydrocarbyl-substituted phenol, an aldehyde, and an
amine or ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted
phenol can have 10 to 400 carbon atoms, in another instance 30 to 180 carbon
atoms, and in a further instance 10 or 40 to 110 carbon atoms. This
hydrocarbyl
substituent can be derived from an olefin or a polyolefin. Useful olefins
include
alpha-olefins, such as 1-decene, which are commercially available.
The polyolefins which can form the hydrocarbyl substituent can be
prepared by polymerizing olefin monomers by well known polymerization
methods and are also commercially available. The olefin monomers include
monoolefins, including monoolefins having 2 to 10 carbon atoms such as
ethylene, propylene, 1-butene, isobutylene, and 1-decene. An especially useful
monoolefin source is a C4 refinery stream having a 35 to 75 weight percent
butene content and a 30 to 60 weight percent isobutene content. Useful olefin
monomers also include diolefins such as isoprene and 1,3-butadiene. Olefin
monomers can also include mixtures of two or more monoolefins, of two or
more diolefins, or of one or more monoolefins and one or more diolefins.
Useful polyolefins include polyisobutylenes having a number average
molecular weight of 140 to 5000, in another instance of 400 to 2500, and in a
further instance of 140 or 500 to 1500. The polyisobutylene can have a
vinylidene double bond content of 5 to 69 percent, in a second instance of 50
to
69 percent, and in a third instance of 50 to 95 percent. The polyolefin can be
a
homopolymer prepared from a single olefin monomer or a copolymer prepared
from a mixture of two or more olefin monomers. Also possible as the
hydrocarbyl substituent source are mixtures of two or more homopolymers, two
or more copolymers, or one or more homopolymers and one or more
copolymers.
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The hydrocarbyl-substituted phenol can be prepared by alkylating
phenol with an olefin or polyolefin described above, such as a polyisobutylene
or polypropylene, using well-known alkylation methods.
The aldehyde used to form the Mannich detergent can have 1 to 10
carbon atoms, and is generally formaldehyde or a reactive equivalent thereof
such as formalin or paraformaldehyde.
The amine used to form the Mannich detergent can be a monoamine or a
polyamine, including alkanolamines having one or more hydroxyl groups, as
described in greater detail above. Useful amines include those described
above,
such as ethanolamine, diethanolamine, methylamine, dimethylamine,
ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2-(2-
aminoethylamino) ethanol. The Mannich detergent can be prepared by reacting
a hydrocarbyl-substituted phenol, an aldehyde, and an amine as described in
U.S. Patent No. 5,697,988. In one embodiment of this invention the Mannich
reaction product is prepared from an alkylphenol derived from a
polyisobutylene, formaldehyde, and an amine that is a primary monoamine, a
secondary monoamine, or an alkylenediamine, in particular, ethylenediamine or
dimethylamine.
The Mannich reaction product of the present invention can be prepared
by reacting the alkyl-substituted hydroxyaromatic compound, aldehyde and
polyamine by well known methods including the method described in U.S.
Patent 5,876,468.
The Mannich reaction product can be prepared by well known methods
generally involving reacting the hydrocarbyl substituted hydroxy aromatic
compound, an aldehyde and an amine at temperatures between 50 to 200 C in
the presence of a solvent or diluent while removing reaction water as
described
in U. S. Patent No. 5,876,468.
Another type of detergent, which can be used in the present invention, is
a succinimide. Succinimide detergents are well known in the field of
lubricants
and include primarily what are sometimes referred to as "ashless" detergents
because they do not contain ash-forming metals and they do not normally
contribute any ash forming metals when added to a lubricant. Succinimide
detergents are the reaction product of a hydrocarbyl substituted succinic
acylating agent and an amine containing at least one hydrogen attached to a
nitrogen atom. The term "succinic acylating agent" refers to a hydrocarbon-
substituted succinic acid or succinic acid-producing compound (which term
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also encompasses the acid itself). Such materials typically include
hydrocarbyl-
substituted succinic acids, anhydrides, esters (including half esters) and
halides.
Succinic based detergents have a wide variety of chemical structures
including typically structures such as
O O
Ri-CH-C C-CH-Ri
N-[R2 -NH]X-R2 -N
/ \
Hz-C C- Hz
O O
In the above structure, each R' is independently a hydrocarbyl group,
which may be bound to multiple succinimide groups, typically a polyolefin-
derived group having an M. of 500 or 700 to 10,000. Typically the
hydrocarbyl group is an alkyl group, frequently a polyisobutylene group with a
molecular weight of 500 or 700 to 5000, or 1500 or 2000 to 5000.
Alternatively expressed, the R' groups can contain 40 to 500 carbon atoms or
at
least 50 to 300 carbon atoms, e.g., aliphatic carbon atoms. The R2 are
alkylene
groups, commonly ethylene (C2H4) groups. Such molecules are commonly
derived from reaction of an alkenyl acylating agent with a polyamine, and a
wide variety of linkages between the two moieties is possible beside the
simple
imide structure shown above, including a variety of amides and quaternary
ammonium salts. Succinimide detergents are more fully described in U.S.
Patents 4,234,435, 3,172,892, and 6,165,235.
The polyalkenes from which the substituent groups are derived are
typically homopolymers and interpolymers of polymerizable olefin monomers
of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms.
The olefin monomers from which the polyalkenes are derived are
polymerizable olefin monomers characterized by the presence of one or more
ethylenically unsaturated groups (i.e., >C=C<); that is, they are mono-
olefinic
monomers such as ethylene, propylene, 1-butene, isobutene, and 1-octene or
polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene,
and isoprene. These olefin monomers are usually polymerizable terminal
olefins; that is, olefins characterized by the presence in their structure of
the
group >C=CH2. Relatively small amounts of non-hydrocarbon substituents can
be included in the polyolefin, provided that such substituents do not
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substantially interfere with formation of the substituted succinic acid
acylating
agents.
Each R' group may contain one or more reactive groups, e.g., succinic
groups, thus being represented (prior to reaction with the amine) by
structures
such as
Ri-(-CH-COOH )y and Ri-(-CH-CO )y
O
CH2-COOH CH2-CO
in which y represents the number of such succinic groups attached to the R'
group. In one type of detergent, y = 1. In another type of detergent, y is
greater than 1, in one embodiment greater than 1.3 or greater than 1.4; and in
another embodiment y is equal to or greater than 1.5. in one embodiment y is
1.4 to 3.5, such as 1.5 to 3.5 or 1.5 to 2.5. Fractional values of y, of
course, can
arise because different specific R' chains may be reacted with different
numbers of succinic groups.
The amines which are reacted with the succinic acylating agents to form
the carboxylic detergent composition can be monoamines or polyamines. In
either case they will be characterized by the formula R4RsNH wherein R4
and R 5 are each independently hydrogen, hydrocarbon, amino-substituted
hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted
hydrocarbon, amino, carbamyl, thiocarbamyl, guanyl, or acylimidoyl groups
provided that no more than one of R4 and R5 is hydrogen. In all cases,
therefore, they will be characterized by the presence within their structure
of at
least one H-N< group. Therefore, they have at least one primary (i.e., H2N-)
or
secondary amino (i.e., H-N<) group. Examples of monoamines include
ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine,
isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine,
oleylamine, N-methyl-octylamine, dodecylamine, and octadecylamine.
The polyamines from which the detergent is derived include principally
alkylene amines conforming, for the most part, to the formula
A N-(alkylene-N)t -H
A A
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wherein t is an integer typically less than 10, A is hydrogen or a hydrocarbyl
group typically having up to 30 carbon atoms, and the alkylene group is
typically an alkylene group having less than 8 carbon atoms. The alkylene
amines include principally, ethylene amines, hexylene amines, heptylene
amines, octylene amines, other polymethylene amines. They are exemplified
specifically by: ethylene diamine, diethylene triamine, triethylene tetramine,
propylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine, di(-trimethylene) triamine.
Higher homologues such as are obtained by condensing two or more of the
above-illustrated alkylene amines likewise are useful. Tetraethylene pentamine
is particularly useful.
The ethylene amines, also referred to as polyethylene polyamines, are
especially useful. They are described in some detail under the heading
"Ethylene Amines" in Encyclopedia of Chemical Technology, Kirk and
Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).
Hydroxyalkyl-substituted alkylene amines, i.e., alkylene amines having
one or more hydroxyalkyl substituents on the nitrogen atoms, likewise are
useful. Examples of such amines include N-(2-hydroxyethyl)ethylene diamine,
N,N"-bis(2-hydroxyethyl)-ethylene diamine, 1-(2-hydroxyethyl)piperazine,
monohydroxypropyl)-piperazine, di-hydroxypropy-substituted tetraethylene
pentamine, N-(3-hydroxypropyl)-tetra-methylene diamine, and 2-heptadecyl-l-
(2-hydroxyethyl)-imidazoline.
Higher homologues, such as are obtained by condensation of the above-
illustrated alkylene amines or hydroxy alkyl-substituted alkylene amines
through amino radicals or through hydroxy radicals, are likewise useful.
Condensed polyamines are formed by a condensation reaction between at least
one hydroxy compound with at least one polyamine reactant containing at least
one primary or secondary amino group and are described in U.S. Patent
5,230,714 (Steckel).
The succinimide detergent is referred to as such since it normally
contains nitrogen largely in the form of imide functionality, although it may
be
in the form of amine salts, amides, imidazolines as well as mixtures thereof.
To prepare the succinimide detergent, one or more of the succinic acid-
producing compounds and one or more of the amines are heated, typically with
removal of water, optionally in the presence of a normally liquid,
substantially
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inert organic liquid solvent/diluent at an elevated temperature, generally in
the
range of 80 C up to the decomposition point of the mixture or the product;
typically 100 C to 300 C.
The succinic acylating agent and the amine (or organic hydroxy
compound, or mixture thereof) are typically reacted in amounts sufficient to
provide at least one-half equivalent, per equivalent of acid-producing
compound, of the amine (or hydroxy compound, as the case may be).
Generally, the maximum amount of amine present will be about 2 moles of
amine per equivalent of succinic acylating agent. For the purposes of this
invention, an equivalent of the amine is that amount of the amine
corresponding
to the total weight of amine divided by the total number of nitrogen atoms
present. The number of equivalents of succinic acid-producing compound will
vary with the number of succinic groups present therein, and generally, there
are two equivalents of acylating reagent for each succinic group in the
acylating
reagents. Additional details and examples of the procedures for preparing the
succinimide detergents of the present invention are included in, for example,
U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 4,234,435; 6,440,905 and
6,165,235.
Yet another type of detergent, which can be used in the present invention,
can be a polyisobutylene amine. The amine use to make the the polyisobutylene
amine can be a polyamine such as ethylenediamine, 2-(2-aminoethylamino)-
ethanol, or diethylenetriamine. The polyisobutylene amine of the present
invention can be prepared by several known methods generally involving
amination of a derivative of a polyolefin to include a chlorinated polyolefin,
a
hydroformylated polyolefin, and an epoxidized polyolefin. In one embodiment
of the invention the polyisobutylene amine is prepared by chlorinating a
polyolefin such as a polyisobutylene and then reacting the chlorinated
polyolefin with an amine such as a polyamine at elevated temperatures of
generally 100 to 150 C as described in U. S. Patent No. 5,407,453. To improve
processing a solvent can be employed, an excess of the amine can be used to
minimize cross-linking, and an inorganic base such as sodium carbonate can be
used to aid in removal of hydrogen chloride generated by the reaction.
Yet another type of detergent, which can be used in the present invention, is
a glyoxylate. A glyoxylate detergent is a fuel soluble ashless detergent
which, in a
first embodiment, is the reaction product of an amine having at least one
basic
nitrogen, i.e. one >N-H, and a hydrocarbyl substituted acylating agent
resulting from
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the reaction, of a long chain hydrocarbon containing an olefinic bond with at
least
one carboxylic reactant selected from the group consisting of compounds of the
formula (I)
(RiC(O)(R2)õC(O))R3 (I)
and compounds of the formula (II)
OR4
R1-C (R2)n-C(O)OR3
I
OH (II)
wherein each of Ri, R3 and R4is independently H or a hydrocarbyl group, R2 is
a
divalent hydrocarbylene group having 1 to 3 carbons and n is 0 or 1:
Examples of carboxylic reactants are glyoxylic acid, glyoxylic acid methyl
ester methyl hemiacetal, and other omega-oxoalkanoic acids, keto alkanoic
acids
such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids and
numerous others. The skilled worker having the disclosure before him will
readily
recognize the appropriate compound of formula (I) to employ as a reactant to
generate a given intermediate.
The hydrocarbyl substituted acylating agent can be the reaction of a long
chain hydrocarbon containing an olefin and the above described carboxylic
reactant
of formula (I) and (II), further carried out in the presence of at least one
aldehyde or
ketone. Typically, the aldehyde or ketone contains from 1 to about 12 carbon
atoms.
Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde,
butyraldehyde, isobutyraldehyde, pentanal, hexanal. heptaldehyde, octanal,
benzaldehyde, and higher aldehydes. Other aldehydes, such as dialdehydes,
especially glyoxal, are useful, although monoaldehydes are generally
preferred.
Suitable ketones include acetone, butanone, methyl ethyl ketone, and other
ketones.
Typically, one of the hydrocarbyl groups of the ketone is methyl. Mixtures of
two
or more aldehydes and/or ketones are also useful.
Compounds and the processes for making these compounds are disclosed in
U.S. Pat. Nos. 5,696,060; 5,696,067; 5,739,356; 5,777,142; 5,856,524;
5,786,490;
6,020,500; 6,114,547; 5,840,920 and are incorporated herein by reference.
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In another embodiment, the glyoxylate detergent is the reaction product of an
amine having at least one basic nitrogen, i.e. one >N-H, and a hydrocarbyl
substituted acylating agent resulting from the condensation product of a
hydroxyaromatic compound and at least one carboxylic reactant selected from
the
group consisting of the above described compounds of the formula (I) and
compounds of the formula (II). Examples of carboxylic reactants are glyoxylic
acid,
glyoxylic acid methyl ester methyl hemiacetal, and other such materials as
listed
above.
The hydroxyaromatic compounds typically contain directly at least one
hydrocarbyl group R bonded to at least one aromatic group. The hydrocarbyl
group
R may contain up to about 750 carbon atoms or 4 to 750 carbon atoms, or 4 to
400
carbon atoms or 4 to 100 carbon atoms. In one embodiment, at least one R is
derived from polybutene. In another embodiment, R is derived from
polypropylene.
In another embodiment, the reaction of the hydroxyaromatic compound and
the above described carboxylic acid reactant of formula (I) or (II) can be
carried out
in the presence of at least one aldehyde or ketone. The aldehyde or ketone
reactant
employed in this embodiment is a carbonyl compound other than a carboxy-
substituted carbonyl compound. Suitable aldehydes include monoaldehydes such
as
formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde,
pentanal, hexanal, heptaldehyde, octanal, benzaldehyde, and higher aldehydes.
Other aldehydes, such as dialdehydes, especially glyoxal, are useful. Suitable
ketones include acetone, butanone, methyl ethyl ketone, and other ketones.
Typically, one of the hydrocarbyl groups of the ketone is methyl. Mixtures of
two
or more aldehydes and/or ketones are also useful.
Compounds and the processes for making these compounds are
disclosed in U.S. Pat. Nos. 3,954,808; 5,336,278; 5,620,949 and 5,458,793 and
are incorporated herein by reference
The detergent additive of this invention can be present in a mixture of
various detergents referenced above.
In one embodiment, the detergent in the fuel composition may be
present in an amount from about 1 to about 10000 ppm, or about 5 to about
5000, or about 20 to about 4000 or about 40 to about 3500 ppm.
In one embodiment, the detergent can be present in the fuel additive
concentration in an amount from about 1 to about 99 percent by weight, or
about 10 to about 80 percent by weight, or about 20 to about 60 percent by
weight, or about 20 to about 50 percent by weight.
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Friction Modifier
The present invention can comprise a friction modifier. The friction
modifier is selected from the group consisting of an alkoxyalted fatty amine,
fatty acid or derivative thereof, and mixtures thereof.
In one embodiment, the friction modifier of the present invention can
include an alkoxylated fatty amine, which can include amines represented by
the formula:
(A10),,H
RN
~(A2 O)yH
wherein R is a hydrocarbyl group having about 4 to 30 carbon atoms, A'
and A2 are vicinal alkylene groups, and the sum of x and y is an integer that
is
at least 1. The hydrocarbyl group is a univalent radical of carbon atoms that
is
predominantly hydrocarbon in nature, but can have nonhydrocarbon substituent
groups and can have heteroatoms. The hydrocarbyl group R can be an alkyl or
alkylene group of about 4 to 30 carbon atoms, or about 10 to 22 carbon atoms.
The vicinal alkylene groups A' and A2 can be the same or different and
include:
ethylene(-CH2-), propylene (-CH2CH2CH2-) and butylene (-
CH2CH2CH2CH2-) having the carbon to nitrogen and carbon to oxygen bonds
on adjacent or neighboring carbon atoms. Examples of alkoxylated fatty
amines can include: diethoxylated tallowamine, diethoxylated oleylamine,
diethoxylated stearylamine, and the diethoxylated amine from soybean oil fatty
acids. Alkoxylated fatty amines are commercially available from Akzo under
the Ethomeen series.
In one embodiment, the friction modifier of the present invention can
include a fatty acid or derivative thereof. The fatty acid or derivative
thereof
can have about 4 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22
carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and
include capric, lauric, myristic, palmitic, stearic, behenic, oleic,
petroselinic,
elaidic, palmitoleic, linoleic, linolenic and erucic acid. Typical fatty acids
are
those derived from natural oil typically containing C6 or C22 fatty acid
esters,
i.e., glycerol fatty acid esters or triglycerides derived from natural
sources, for
use herein include, but are not limited to beef tallow oil, lard oil, palm
oil,
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castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, sunflower oil,
olive
oil, whale oil, coconut oil, palm oil, rape oil, and soya oil.
In another embodiment of this invention, the fatty acid can be the partial
ester of a fatty carboxylic acid. The partial ester of the present invention
has at
least one free hydroxyl group and is formed by reacting at least one fatty
carboxylic acid and at least one polyhydric alcohol.
The fatty carboxylic acid used to form the partial ester can be saturated
or unsaturated aliphatic, can be branched or straight chain, can be a
monocarboxylic or polycarboxylic acid, and can be a single acid or mixture of
acids. The fatty carboxylic acid can have about 4 to 30 carbon atoms, or 8 to
26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated
monocarboxylic acids are useful and include capric, lauric, myristic,
palmitic,
stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic,
linolenic and
erucic acid.
The polyhydric alcohol used to form the partial ester has two or more
hydroxyl groups and includes alkylene glycols, polyalkylene glycols, triols,
polyols having more than three hydroxyl groups, and mixtures thereof.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol,
neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, and
sorbitol.
The partial esters having at least one free hydroxyl group are
commercially available or can be formed by a variety of methods well known in
the art. These esters are derived from any of the above described fatty
carboxylic acids and polyhydric alcohols or mixtures thereof. Preferred esters
are derived from fatty carboxylic acids having about 12 to 22 carbon atoms and
glycerol, and will usually be mixtures of mono- and diglycerides, such as, a
mixture of glycerol monooleate and glycerol dioleate. In one embodiment, the
friction modifier of the present invention is glycerol monooleate.
Another derivative of the fatty carboxylic acid is the amide of the fatty
carboxylic acid. In general, these compounds are the reaction product of the
natural fatty acid oils containing 6 to 22 carbon atoms and an amine. The
fatty
carboxylic acid of these amides can be saturated or unsaturated aliphatic, can
be branched or straight chain, can be a monocarboxylic or polycarboxylic acid,
and can be a single acid or mixture of acids. The fatty carboxylic acid can
have
about 6 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms.
Saturated and unsaturated monocarboxylic acids are useful and include capric,
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lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic,
palmitoleic, linoleic, linolenic and erucic acid.
The amine can be an alkyl amine having from about 2 to about 10
carbon atoms, or about 4 to about 6 carbon atoms. A typical amine can be the
alkanol amines. The alkanolamine used in the reaction with the fatty acid can
be a primary or secondary amine, which possesses at least one hydroxy group.
The alkanolamine corresponds to the general formula HN(RiOH)z-xHx wherein
Ri is a lower hydrocarbyl having from about two to about six carbon atoms and
x is 0 or 1. The expression "alkanolamine" is used in its broadest sense to
include compounds containing at least one primary or secondary amine and at
least one hydroxy group, such as, for example, monoalkanolamines,
dialkanolamines, and so forth. It is believed that almost any alkanolamine can
be used, although preferred alkanolamines are lower alkanolamines having
form about two to about six carbon atoms. The alkanolamine can possess an 0
or N functionality, in addition to the one amino group (that group being a
primary of secondary amino group), and at least one hydroxy group. Suitable
alkanolamines for use herein include: mono ethano lamine, diethanolamine,
propanolamine, isopropanolamine, dipropanolamine, di-isopropanolamine,
butanolamines, aminoethylaminoethanols, e.g., 2-(2-aminoethylamino)ethanol,
and the like with diethanolamine being preferred. It is also contemplated that
mixtures of two or more alkanolamines can be employed.
In one embodiment, the friction modifier can be present in the fuel
additive concentrate in an amount from about 1 to about 99 percent by weight,
or about 2 to about 50 percent by weight, or about 5 to about 40 percent by
weight, or about 5 to about 30 percent by weight, in yet another embodiment
from about 8 to about 25 percent by weight.
In one embodiment, the friction modifier of this invention can be
present in a fuel composition on a weight basis from about 1 to about 10,000
ppm (parts per million), and in other embodiment from about 5 to about 8,000
ppm, or about 10 to about 7000 ppm, or about 20 to about 5000 ppm, or about
30 to about 2000 ppm, or about 50 to about 1500, or about 40 to about 1000
ppm, or about 40 to about 650 ppm.
Antioxidant
The present invention can include one or more antioxidants. The
antioxidants for use in the present invention are well known and include a
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variety of chemical types including phenate sulfides, phosphosulfurized ter-
penes, sulfurized esters, aromatic amines, and hindered phenols. In one em-
bodiment, the present invention can contain an antioxidant selected from the
group consisting of hindered phenol or derivatives thereof, aromatic amines or
derivatives thereof, and mixtures thereof.
Aromatic amines are typically of the formula
NHR5
6 R6
wherein R5 is a phenyl group or a phenyl group substituted by R', and R6 and
R7 are independently a hydrogen or an alkyl group containing 1 to 24 carbon
atoms. Preferably R5 is a phenyl group substituted by R' and R6 and R' are
alkyl groups containing from 4 to 20 carbon atoms. In one embodiment, the
antioxidant can be an alkylated diphenylamine, such as, nonylated diphenyl-
amine containing typically some of the formula
r
C9H19 OD - 0- C9H19
Hindered phenol antioxidants are typically alkyl phenols of the formula
H
~ (R4)m
wherein R4 is an alkyl group containing 1 to 24 carbon atoms and m is an
integer of 1 to 5. In certain embodiments, R4 contains 4 to 18 carbon atoms or
4 to 12 carbon atoms. R4 may be either straight chained or branched chained,
especially branched. Suitable values of m include 1 to 4, such as 1 to 3 or,
particularly, 2. In certain well-known embodiments, the phenol is a butyl
substituted phenol containing 2 or 3 t-butyl groups. When a is 2, the t-butyl
groups may occupy the 2,6-positions, that is, the phenol is sterically
hindered:
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H
0
The antioxidant can be, and typically is, further substituted at the 4-
position
with any of a number of substituents, such as hydrocarbyl groups or groups
bridging to another hindered phenolic ring.
Also included among the antioxidants are hindered ester substituted
phenols such as those represented by the formula:
t-alkyl
II
HO CH2CH2COR3
t-alkyl
wherein t-alkyl can be, among others, t-butyl, R3 is a straight chain or
branched
chain alkyl group containing about 1 to about 22 carbon atoms, or about 2 to
about 22, or about 2 to about 8, or about 4 to about 8 carbon atoms. R3 may be
a 2-ethylhexyl group, isooctyl or an n-butyl or n-octyl group. Hindered ester
substituted phenols can be prepared by heating a 2,6-dialkylphenol with an
acrylate ester under base catalysis conditions, such as, aqueous KOH.
The antioxidants of the present invention can also include sulfurized
olefins, such as, mono-, or disulfides or mixtures thereof. These materials
generally have sulfide linkages having 1 to 10 sulfur atoms, or 1 to 4, or 1
or 2
sulfur atoms. Materials, which can be sulfurized to form the sulfurized
organic
compositions of the present invention, include: oils, fatty acids and esters,
olefins and polyolefins made thereof, terpenes, or Diels-Alder adducts.
Details
of methods of preparing some such sulfurized materials can be found in U.S.
Pat. Nos. 3,471,404 and 4,191,659. Molybdenum compounds can also serve as
antioxidants. The use of molybdenum and sulfur containing compositions as
antioxidants is known.
In certain embodiment, a mixture of antioxidants are employed, such as,
both a phenolic and an aromatic amine antioxidant, or mixtures thereof, or
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alternatively phenolic, or aromatic amine, or phosphosulfurized olefin
antioxidants or molybdenum antioxidant or mixtures thereof.
In one embodiment, the amount of the antioxidant in the fuel
composition can be present in an amount from about 1 to about 1000 ppm, or
about 1 to about 5000, or about 2 to about 500, or about 4 to about 200 or
about
5 to about 100 ppm.
In one embodiment, the amount of antioxidant can be present in the fuel
additive concentration in an amount from about 1 to about 99 percent by
weight, or from about 1 to about 40 percent by weight, or from about 2 to
about
30 percent by weight, or from about 2 to about 20 percent by weight.
Fuel Composition
In one embodiment, the fuel composition contains a fuel, which is a
liquid at room temperature, and an additive wherein the additive is selected
from the group consisting of: a detergent; antioxidant; friction modifier se-
lected from the group consisting of an alkoxylated fatty amine, a fatty acid
or
derivative thereof, and mixture thereof; and mixtures thereof; wherein the
detergent is soluble in a nonhydrocarbonaceous fuel. The fuel, which is a
liquid
at room temperature, and additives of the fuel composition are described
above.
Fuel Additive Concentrate
In one embodiment, the fuel additive concentrate of the present
invention can be present in a fuel in an amount from about 1 to about 10000
ppm, in another embodiment about 5 to about 8000 ppm, in another
embodiment about 10 to about 5000 ppm or about 20 to about 5000 ppm, in yet
another embodiment about 100 to about 4000 ppm, and in another embodiment
about 200 to about 2000, or about 300 to about 2000 or about 300 to aboutl000
ppm.
Miscellaneous
The fuel additive concentrate compositions and fuel compositions of the
present invention can contain other additives that are well known to those of
skill in the art. These can include corrosion inhibitors, dyes, bacteriostatic
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agents, auxiliary, gum inhibitors, marking agents, metal deactivators,
detergents, demulsifiers, or mixtures thereof.
Industrial Application
In one embodiment the present invention can be used in an internal
combustion engine. The internal combustion engine includes a 2-stroke or 4-
stroke engine fuelled with alcohol. The internal combustion engine includes a
direct injection or spark ignited engine.
As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the
art. Specifically, it refers to a group having a carbon atom directly attached
to
the remainder of the molecule and having predominantly hydrocarbon
character. Examples of hydrocarbyl groups include: hydrocarbon substituents,
that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-
substituted
aromatic substituents, as well as cyclic substituents wherein the ring is
completed through another portion of the molecule (e.g., two substituents
together form a ring); substituted hydrocarbon substituents, that is,
substituents
containing non-hydrocarbon groups which, in the context of this invention, do
not alter the predominantly hydrocarbon nature of the substituent (e.g., halo
(especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto,
nitro,
nitroso, and sulfoxy); hetero substituents, that is, substituents which, while
having a predominantly hydrocarbon character, in the context of this
invention,
contain other than carbon in a ring or chain otherwise composed of carbon
atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass
substituents as pyridyl, furyl, thienyl and imidazolyl. In general, no more
than
two, preferably no more than one, non-hydrocarbon substituent will be present
for every ten carbon atoms in the hydrocarbyl group; typically, there will be
no
non-hydrocarbon substituents in the hydrocarbyl group.
It is known that some of the materials described above may interact in
the final formulation, so that the components of the final formulation may be
different from those that are initially added. For instance, metal ions (of,
e.g., a
detergent) can migrate to other acidic or anionic sites of other molecules.
The
products formed thereby, including the products formed upon employing the
composition of the present invention in its intended use, may not be
susceptible
of easy description. Nevertheless, all such modifications and reaction
products
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are included within the scope of the present invention; the present invention
encompasses the composition prepared by admixing the components described
above.
Each of the documents referred to above is incorporated herein by
reference. Except in the Examples, or where otherwise explicitly indicated,
all
numerical quantities in this description specifying amounts of materials, reac-
tion conditions, molecular weights, number of carbon atoms, and the like, are
to
be understood as modified by the word "about." Unless otherwise indicated,
each chemical or composition referred to herein should be interpreted as being
a commercial grade material which may contain the isomers, by-products,
derivatives, and other such materials which are normally understood to be
present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise indicated. It
is to be understood that the upper and lower amount, range, and ratio limits
set
forth herein may be independently combined. Similarly, the ranges and
amounts for each element of the invention can be used together with ranges or
amounts for any of the other elements. As used herein, the expression
"consisting essentially of' permits the inclusion of substances that do not
materially affect the basic and novel characteristics of the composition under
consideration.
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