Note: Descriptions are shown in the official language in which they were submitted.
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FUEL ADDITIVE COMPOSITION
FIELD OF THE DISCLOSURE
[0001] The present disclosure generally relates to a fuel additive composition
for improving
the fuel economy of engines and reducing deposits within these engines. The
fuel additive
composition includes a polyalkenylsuccinimide, a polyisobutene amine, and a
carrier oil.
DESCRIPTION OF THE RELATED ART
[0002] Modern vehicles include sophisticated combustion engines, which
optimize
combustion, emissions, performance, durability, and fuel economy.
Fuel additive
compositions (e.g. gasoline performance packages), which include fuel economy
and
additional fuel additives, such as detergents, can be added to fuel to further
optimize
combustion, emissions, performance, durability, and fuel economy of such
engines.
[0003] These engines typically include one or more pistons which are located
inside a
cylinder. Fuel and air is introduced into the cylinder and ignited to move the
piston and
power the engine. Fuel economy additives reduce friction between the piston
and the
cylinder and thus reduce fuel consumption and improve the fuel economy of the
engine.
[0004] Fuel additive compositions may include fuel additives such as the
reaction products of
a carbonic acid or a derivative thereof and a polyalcohol and/or alkanol
amine, and fatty acid
amides and propoxylated fatty acid amides. Fuel additive compositions may also
include
various fuel additives such as polyalkene amines and polyalkenylsuccinimides.
Fuel additive
compositions may further include various carrier oils known in the art,
including mineral oils
and synthetic oils.
[0005] However, fuel additive compositions comprising fuel additives such as
those set forth
above, e.g. polyalkenylsuccinimide, etc., are generally immiscible with one
another. As such,
fuel additive compositions that include such fuel additives can often be non-
homogeneous
and non-pumpable or may even form precipitates, separate into two phases,
and/or solidify
over various times and at various temperatures.
[0006] Because it is technically and commercially desirable that such fuel
additive
compositiOns be homogeneous and pumpable over a broad range of temperatures,
even at
temperatures as low as -20 C, solubilizers have been used to improve
miscibility of additives
and the homogeneity of fuel additive compositions formed therefrom. However,
these
solubilizers are costly and do not typically contribute to performance
improvement of
engines. In some cases these solubilizers can even cause negative side effects
such as poor
seal compatibility, oil dilution, and higher levels of combustion chamber
deposits. Such
deposits can cause enrichment of fuel to air ratios in engines which result in
increased
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hydrocarbon and carbon monoxide emissions, driving problems such as rough
idling and
frequent stalling, reduced fuel economy, and decreased engine life.
[0007] As such, there remains an opportunity to develop improved fuel
additives which are
miscible with additional fuel additives, and also an opportunity to develop
fuel additive
compositions formed with the improved fuel additives that are stable over a
broad range of
temperatures and conditions and that improve the fuel economy of internal
combustion
engines.
SUMMARY OF THE DISCLOSURE AND ADVANTAGES
[0008] In some aspects, a fuel additive composition includes a
polyalkenylsuccinimide, a
mono or polyfunctional polyisobutene amine, and a carrier oil selected from
the group of
mineral oils, polyethers, polyetheramines, esters, and combinations thereof.
The
polyalkenylsuccinimide itself includes the reaction product of a hydrocarbyl
dicarboxylic
acid producing reaction intermediate and a nucleophilic reactant.
The hydrocarbyl
dicarboxylic acid producing reaction intermediate includes the reaction
product of a
polyolefin comprising C2 to C18 olefin units and having a number average
molecular weight
(Mn) of about 500 to 5,000 g/mol and a C4 to C10 monounsaturated acid
reactant. The
hydrocarbyl dicarboxylic acid producing reaction intermediate includes from
0.5 to 10
dicarboxylic acid producing moieties per molecule of the polyolefin. The
nucleophilic
reactant is selected from the group of amines, alcohols, amino alcohols, and
combinations
thereof.
[0009] The polyalkenylsuccinimide improves the fuel economy of internal
combustion
engines when added to fuel yet is miscible with the polyisobutene amine and
the carrier oil
included in the fuel additive compositions. As such, the fuel additive
compositions possess
excellent storage stability and remain homogenous over a wide range of times
and
temperatures and do not require inclusion of a solubilizer. Further, the fuel
additive
compositions can be added to fuel in minimal amounts to improve fuel economy
and reduce
engine deposits and emissions.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0010] In some aspects, the present disclosure provides fuel additive
compositions
("compositions"). The compositions include: (A) a polyalkenylsuccinimide, (B)
a mono or
polyfunctional polyisobutene amine, and (C) a carrier oil. The compositions
can be used in
fuels, such as diesel fuels, gasoline, kerosene or middle distillates, and
heating oil, and can
also be used as an additive in lubricants. The compositions can be used as a
fully formulated
fuel additive composition, which can be added to fuel to reduce fuel
consumption and thus
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improve fuel economy of an internal combustion engine. As a fuel additive, the
compositions
also reduce deposits in carburetors, fuel intake systems, and engines, reduce
emissions, and
improve engine performance.
The PolvalkenvIsuccinimide (A)
[0011] In some embodiments, the polyalkenylsuccinimide (A) includes the
reaction product
of: (1) a hydrocarbyl dicarboxylic acid producing reaction intermediate and
(2) a nucleophilic
reactant.
The Hydrocarbyl Dicarboxvlic Acid Producing Reaction Intermediate (A.1)
[0012] In some embodiments, the reaction intermediate (A.1) includes the
reaction product
of: (A.1.a) a polyolefin comprising C2 to C18 olefin units and having a number
average
molecular weight (Mn) of about 500 to 5,000 g/mol and (A.1.b) a C4 to CHI
monounsaturated
acid reactant. The polyolefin (A.1.a) and the C4 to Ci0 monounsaturated acid
reactant (A.1.b)
can be reacted by way of various reaction mechanisms under various conditions
to form the
reaction intermediate (A.1).
[0013] For example, the reaction intermediate (A.1) can be formed via an "ene"
reaction by
heating a mixture of the polyolefin (Ala) and the C4 to CIO monounsaturated
acid reactant
(A.1.b). In such an "ene" reaction, the polyolefin (A.1.a) undergoes an
addition of the C4 to
C10 monounsaturated acid reactant (A.1.b) at a double bond. As another
example, the
polyolefin (A.1.a) can be first halogenated, for example, chlorinated or
brominated with from
1 to 8, alternatively from 3 to 7, weight % chlorine or bromine, based on the
weight of
polyolefin (A.1.a). By passing the chlorine or bromine through the polyolefin
(A.1.a) at a
temperature of from 60 to 160, alternatively from 110 to 130, C for from 0.5
to 10,
alternatively from 1 to 7, hours to form a halogenated polyolefin. The
halogenated polyolefin
is then reacted with the C4 to C10 monounsaturated acid reactant (A.1.b) at a
temperature of
from 100 to 250, alternatively from 180 to 235, C for a time of from 0.5 to
10, alternatively
from 3 to 8, hours, to form the reaction intermediate (A.1).
[0014] The hydrocarbyl dicarboxylic acid producing reaction intermediate (A.1)
can include
a polyolefin substituted with dicarboxylic acid producing moieties.
Specifically, the reaction
intermediate (A.1) is, for example, an acid, an anhydride, or ester which
includes a long chain
hydrocarbon (polyolefin (A.1.a)) substituted with an average of from 0.5 to
10.0,
alternatively from 0.5 to 5, alternatively from 0.7 to 2.0, alternatively from
0.7 to 1.7,
alternatively from 0.9 to 1.7, mol of the C4 to C10 monounsaturated acid
reactant (A.1.b), i.e.,
dicarboxylic acid producing moieties, per mol of polyolefin (A.1.a). In one
embodiment, the
reaction intermediate (A.1) is a polyalkenylsuccinic anhydride, e.g. a
polyisobutenylsuccinic
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anhydride. These functionality ratios of dicarboxylic acid producing moieties
to polyolefin,
e.g. 1.2 to 2.0, etc., are based upon the total amount of polyolefin (A.1.a)
that is present in the
resulting product formed in the aforementioned reactions.
The Polvolefin (A.1.a)
[0015] The polyolefin (A.1.a) of the subject disclosure includes C2 to C18,
alternatively C2 to
Cio, alternatively C2 to C8, alternatively C2 to C6, olefin units. Non-
limiting examples of
olefin units include ethylene, propylene, butylene, isobutylene, pentene,
octene-1, and
styrene. In some embodiments, the polyolefin (A.1.a) is a polyalkene. The
polyolefin
(A.1.a) can be homopolymer, such as polyisobutylene, or copolymer of two or
more of
different olefin units. Non-limiting examples of copolymers which can be used
to form the
polyolefin (A.1.a) include ethylene and propylene, butylene and isobutylene,
propylene and
isobutylene. Additional non-limiting examples of copolymers include copolymers
that
include a minor molar amount of olefin units, e.g. 1 to 10 mol %, are C4 to
C18 non-
conjugated diolefin units such as a copolymer of isobutylene and butadiene or
a copolymer of
ethylene, propylene, and 1,4-hexadiene.
[0016] The polyolefin (A.1.a) can be linear or branched. In some embodiments,
the
polyolefin (Ala) has a number average molecular weight (Mn) of from 500 to
5,000,
alternatively from 750 to 4,000, alternatively from 1,000 to 3,000,
alternatively from 1,000 to
2,000, g/mol.
[0017] The polyolefin (A.1.a) can be saturated or unsaturated. One non-
limiting example of
the polyolefin (A.1.a) which is saturated is an ethylene-propylene copolymer
made by a
Ziegler-Natta synthesis using hydrogen as a moderator to control molecular
weight. In some
embodiments, the polyolefin (A.1.a) is unsaturated. In some embodiments, the
polyolefin
(A.1.a) includes a terminal double bond.
[0018] To this end, in one embodiment, the polyolefin (A.1.a) is a first
reactive
polyisobutene. The first reactive polyisobutene is a highly reactive
polyisobutene which has
a high content of terminal ethylenic double bonds. Terminal double bonds are
alpha-olefinic
double bonds, e.g. vinylidene double bonds. The first reactive polyisobutene
can have a
content of terminal double bonds of greater than 50, alternatively greater
than 70,
alternatively greater than 75, alternatively greater than 80, alternatively
greater than 85, mol
%. The first reactive polyisobutene can have a uniform polymer backbone which
includes
greater than 85, alternatively greater than 90, alternatively greater than 95,
% by weight of
isobutene units.
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[0019] The first reactive polyisobutene can have a number average molecular
weight (Mn) of
from 500 to 5,000, alternatively from 800 to 4,000, alternatively from 800 to
3,000,
alternatively from 800 to 2,000, g/mol. The dispersity D (Mw/Mõ), i.e., the
quotient of the
weight average molecular weight Mw divided M, of the first reactive
polyisobutene is less
than 7, alternatively less than 3, alternatively from 1.05 to 7. In some
embodiments, the
dispersity D (Mw/Mn) of the first reactive polyisobutene is less than 3. In
some embodiments,
the first reactive polyisobutene has a dispersity of less than 2.0 for M,,
less than or equal to
2,000, and a dispersity of less than 1.5 for Mn less than or equal to 1,000.
In some
embodiments, the first reactive polyisobutene is free of organic and inorganic
bases, water,
alcohols, ethers, acids and peroxides.
[0020] Suitable non-limiting examples of the first reactive polyisobutene are
commercially
available from BASF SE under the GLISSOPAL brand of polyisobutenes.
The C4 to C10 Monounsaturated Acid Reactant (A.1.b)
[0021] The C4 to C10 monounsaturated acid reactant (A.1.b) reacts with the
polyolefin (A.1.a)
to form the reaction intermediate (A.1). The C4 to C10 monounsaturated acid
reactant (A.1.b)
is can be an alpha or beta unsaturated C4 to C10 dicarboxylic acid, anhydride
or ester thereof.
Non-limiting examples of the C4 to C10 monounsaturated acid reactant (A.1.b)
include
fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid,
dimethyl
fumarate, chloromaleic an-hydride, and combinations thereof.
[0022] In one embodiment, the C4 to C10 monounsaturated acid reactant (A.1.b)
is selected
from the group of maleic acid, maleic anhydride, functional derivatives
thereof, and
combinations thereof. As used in the above sentence, the term functional
derivative describes
derivatives of maleic acid or maleic anhydride which react with the polyolefin
(A.1.a) to form
the same or a comparable result or product, i.e., the reaction intermediate
(A.1). In the case
of maleic acid, functional derivatives include, for example, monoalkyl
maleates, dialkyl
maleates, maleyl dichloride, maleyl dibromide, maleic acid monoalkyl ester
monochloride, or
maleic acid monoalkyl ester monobromide. The alcohol components, in the case
of the
maleates are, for example, lower alkyl radicals of, for example, 1 to 6, in
particular 1 to 4,
carbon atoms, for example methyl or ethyl. In some embodiments, the C4 to CIO
monounsaturated acid reactant (A.1.b) is maleic anhydride. In one embodiment,
maleic
anhydride is reacted with the first reactive polyisobutene to form the
reaction intermediate
(A.1) comprising polyisobutenylsuccinic anhydride.
The Nucleophilic Reactant (A.2)
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[0023] As set forth above, the polyalkenylsuccinimide (A) includes the
reaction product of
the hydrocarbyl dicarboxylic acid producing reaction intermediate (A.1) and
the nucleophilic
reactant (A.2). In some embodiments, the polyalkenylsuccinimide (A) is formed
via a
neutralization reaction of the nucleophilic reactant (A.2) with the
hydrocarbyl dicarboxylic
acid producing reaction intermediate (A.1). The nucleophilic reactant (A.2)
can be selected
from the group of amines, alcohols, amino alcohols, and combinations thereof.
[0024] The nucleophilic reactant (A.2) can be a monoamine, an oligoamine or a
polyamine.
Since tertiary amines are generally unreactive with anhydrides, it is
desirable to have at least
one primary or secondary amine group on the amine.
[0025] The nucleophilic reactant (A.2) can include an amine having Formula Ia
or Ib
immediately below:
R.N/R"
R' (I a)
(CH2)x¨ENH¨(CH2)x _____________________________ N
Y R'
R' (Ib)
wherein R, R', and R" are independently selected from the group consisting of
hydrogen, C1
to C25 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6
alkylene radicals,
C2 to C12 hydroxy amino alkylene radicals, and C1 to C12 alkylamino C2 to C6
alkylene
radicals; each X can be the same or a different number of from 2 to 6,
alternatively from 2 to
4; and Y is a number from 0 to 10, alternatively from 2 to 7, alternatively
from 3 to 7.
[0026] In a some embodiments, the nucleophilic reactant (A.2) includes an
amine having
Formula II:
H2N(CH2)õ-NH-[(CH2)y-NI-1],-(CH2)õNH2 (II)
where x and y are each independently an integer from 1 to 5, alternatively
from 2 to 4, and z
is an integer from 0 to 8, or mixtures thereof
[0027] The nucleophilic reactant (A.2) can include an alkylene polyamine, such
as a
methylenepolyamine, ethylenepolyamine, butylenepolyamine, propylenepolyamine
and
pentylenepolyamine. In various embodiments, the alkylene polyamine from 2 to
40,
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alternatively from 2 to 20, alternatively from 2 to 12, alternatively from 2
to 6, total carbon
atoms and from 1 to 12, alternatively from 2 to 12, alternatively from 2 to 9,
alternatively
from 3 to 9, nitrogen atoms per molecule. To form the polyalkenylsuccinimide
(A) of such
embodiments, from 0.1 to 3.0, alternatively from 0.1 to 2.0, alternatively
from 0.2 to 1.0,
alternatively from 0.2 to 0.6, mol of succinic moieties can be reacted per
equivalent of the
nucleophilic reactant (A.2), e.g. amine, to form the polyalkenylsuccinimide
(A).
[0028] The nucleophilic reactant (A.2) can also include a polyoxyalkylene
polyamine, e.g.
polyoxyalkylene amines, polyoxyalkylene diamines, and polyoxyalkylene
triamines which
have a number average molecular weight (M) of from 200 to about 4000,
alternatively from
400 to 2000, g/mol. Non-limiting examples of polyoxyalkylene polyamines
include the
polyoxyethylene, polyoxypropylene diamines, and the polyoxypropylene triamines
having a
number average molecular weight (Mn) of from 200 to 2000 g/mol.
[0029] The nucleophilic reactant (A.2) can also include a hydrocarbyl amine or
a hydrocarbyl
amine which includes other functional groups, e.g. hydroxy groups, alkoxy
groups, amide
groups, nitriles, imidazoline groups, etc. For example, in one embodiment, the
nucleophilic
reactant (A.2) includes a hydrocarbyl amine with from 1 to 6, alternatively
from 1 to 3,
hydroxy groups. Such amines are capable of reacting with the acid or anhydride
groups of
the reaction intermediate (A.1) via their amine functional groups or the other
functional
groups (described immediately above). Specific, non-limiting examples of the
nucleophilic
reactant (A.2) include hydroxyamines such as 2-amino- 1 -butanol, 2-amino-2-
methy1-1-
propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3 -amino-l-
propanol, 2-amino-
2-methyl- 1,3 -propane-di ol, 2-amino-2-ethyl-1,3-propanediol, N-(beta-hydroxy-
propy1)-N'-
(beta-amino-ethyl)-piperazine, tris(hydroxy-methyl) amino-methane (also known
as
trismethylol--aminomethane), 2-amino- 1 -butanol, ethanolamine, beta-(beta-
hydroxyethoxy)-
ethylamine, and the like.
[0030] The nucleophilic reactant (A.2) can also include an unsaturated alcohol
such as allyl
alcohol, cin-namyl alcohol, propargyl alcohol, 1-cyclohexane-3-o1, and oleyl
alcohol. Still
other classes of the alcohols capable of yielding the polyalkenylsuccinimide
(A) of this
disclosure include ether-alcohols and amino-alcohols, e.g. the oxy-alkylene,
oxy-arylene-,
amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-
alkylene,
amino-alkylene or amino-arylene oxy-arylene radicals exemplified by N,N,N',N'-
tetrahydroxy-trimethylene diamine, and ether-alcohols having up to about 150
oxy-alkylene
radicals in which the alkylene radical includes from 1 to about 8 carbon
atoms.
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[0031] Additional non-limiting examples of the nucleophilic reactant (A.2)
include alicyclic
diamines such as 1,4-di(aminomethyl) cyclo-hexane, and heterocyclic nitrogen
compounds
such as imidazolines, and N-aminoalkyl piperazines. Specific, non-limiting
examples of such
amines include 2-pentadecyl imidazoline, N-(2-aminoethyl) piperazine,
combinations thereof
[0032] In one embodiment, the nucleophilic reactant (A.2) includes a polyamine
selected
from the group of ethylenediamine, triethylenetetramine, propylenediamine,
trimethylenediamine, tripropylenetetramine, tetraethylenepentamine,
hexaethyleneheptamine,
pentaethylenehexamine, and combinations thereof In this embodiment, the
nucleophilic
reactant (A.2) can be the reaction product of ethylene dichloride and ammonia
or the reaction
product of an ethyleneimine with a ring-opening agent, for example water or
ammonia.
[0033] In another embodiment, the nucleophilic reactant (A.2) includes an
ethylene
polyamine, such as diethylene triamine, triethylene tetramine, tetraethylene
pentamine and
pentaethylene hexamine. In this embodiment, the ethylene polyamine can be the
reaction
product of an alkylene chloride with ammonia or an ethylene imine with
ammonia. These
reactions result in a mixture of alkylene polyamines, including cyclic
products such as
piperazines.
[0034] Combinations of the various types and embodiments and examples of the
nucleophilic
reactant (A.2) referenced above can be reacted with the reaction intermediate
(A.1) to form
the polyalkenylsuccinimide (A).
The Polyalkenylsuccinimide (A)
[0035] The polyalkenylsuccinimide (A) of the subject disclosure is broadly
defined herein to
include polyalkenylsuccinimides (e.g. polyisobutenylsuccinimides), diesters of
succinic acids
or acidic esters (e.g. partially esterified succinic acids), and also
partially esterified
polyhydric alcohols or phenols, e.g. esters having free alcohols or phenolic
hydroxyl radicals.
[0036] The polyalkenylsuccinimide (A) can be, or include a
polyisobutenylsuccinimide
which includes monosuccinimides and bissuccinimides. A ratio of
monosuccinimides to
bissuccinimides in the polyisobutenylsuccinimide can be influenced, for
example, by the
varying the molar ratio of the reaction intermediate (A.1), e.g.
polyisobutenylsuccinic
anhydride, to the nucleophilic reactant (A.2), e.g. amine, reacted to form the
polyalkenylsuccinimide (A), e.g. polyisobutenylsuccinimide. The larger the
molar amount of
the reaction intermediate (A.1), e.g. polyisobutenylsuccinic, anhydride in
relation to the
nucleophilic reactant (A.2), e.g. amine, the larger the= resulting amounts of
monosuccinimide,
and vice versa. In order to obtain a higher proportion of monosuccinimide, a
molar ratio of
the reaction intermediate (A.1), e.g. polyisobutenylsuccinic anhydride, to the
nucleophilic
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reactant (A.2), e.g. amine, of from 0.7 to 1.3, alternatively from 0.9 to 1.1,
can be employed.
In order to obtain a higher proportion of bissuccinimide, a molar ratio of the
reaction
intermediate (A.1), e.g. polyisobutenylsuccinic anhydride, to the nucleophilic
reactant (A.2),
e.g. amine, of from 3 to 18, alternativeIy from 2.3 to 1.9, is can be
employed. A
polyalkenylsuccinimide (A), e.g. polyisobutenylsuccinimide, having a higher
monosuccinimide content is particularly suitable as an additive for fuels
(diesel fuel, heating
oil, gasoline fuel), while a polyalkenylsuccinimide (A), e.g.
polyisobutenylsuccinimide,
having a higher content of bissuccinimides is particularly suitable as an
additive for
lubricants.
[0037] To form the polyalkenylsuccinimide (A), the nucleophilic reactant
(A.2), e.g. amines
described above, can be reacted with the reaction intermediate (A.1), e.g.
alkenylsuccinic
anhydride, by heating an oil solution including 5 to 95 weight % of the
reaction intermediate
(A.1) to a temperature of from 100 to 200, alternatively from 125 to 175, C,
for a time of
from 0.5 to 10, alternatively 1 to 6 hours to remove any residual water and
adding the
nucleophilic reactant (A.2). The step of heating the reaction intermediate
(A.1) can facilitate
formation of imides or mixtures of imides and amides, rather than amides and
salts. The
reaction ratios of the reaction intermediate (A.1) to equivalents of amine as
well as the other
nucleophilic reactants (A.2) described herein can vary considerably, depending
upon the
reactants and type of bonds formed. In some embodiments, from 0.1 to 2.0,
alternatively
from 0.1 to 2.0, alternatively from 0.2 to 0.6, mol of dicarboxylic acid
moiety content (e.g.
grafted maleic anhydride content) is used, per equivalent of nucleophilic
reactant (A.2), e.g.
amine. For-example, about 0.8 mol of a pentamine (having two primary amino
groups and 5
equivalents of nitrogen per molecule) can be used to form a mixture of amides
and imides,
the product formed by reacting one mol of olefin with sufficient maleic
anhydride to add 1.6
mol of succinic anhydride groups per mol of olefin, i.e., the pentamine can be
used in an
amount sufficient to provide about 0.4 mol (that is 1.6/(0.8x5) mol) of
succinic anhydride
moiety per, nitrogen equivalent of the amine.
[0038] In one embodiment, the polyalkenylsuccinimide (A) is formed from
polyisobutylene
substituted with succinic anhydride groups and reacted with polyethylene
amines, e.g.
tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxy-
propylene
amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and
pentaerythritol, and
combinations thereof. As one example, the polyalkenylsuccinimide (A) can be
formed by
reacting a polyisobutene substituted with succinic anhydride groups with a
hydroxy
compound, e.g. pentaerythritol, a polyoxyalkylene polyamine, e.g.
polyoxypropylene
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diamine, and a polyalkylene polyamine, e.g. polyethylene diamine and
tetraethylene
pentamine.
[0039] In another embodiment, the polyalkenylsuccinimide (A) includes the
reaction product
of a polyisobutenylsuccinic anhydride, a first amine, and an alcohol. In this
embodiment, the
polyisobutenylsuccinic anhydride, the first amine, and the alcohol are reacted
at a
temperature of from 50 to 200, alternatively 80 to 180, alternatively 80 to
160, alternatively
100 to 160, C to form the polyisobutenylsuccinimide.
[0040] The first amine can have the following formula:
H2N(CH2),-NH-[(CH2)y-NH],-(CH2),NH2
where x and y are each independently an integer from 1 to 5, alternatively
from 2 to 4, and z
is an integer from 0 to 8, or mixtures thereof.
[0041] The alcohol is selected from the group consisting of monohydric
alcohols of the
formula R4OH, where R4 is straight-chain or branched, cyclic or branched
cyclic alkyl of 1 to
16 carbon atoms, and combinations thereof In many embodiments, the alcohol is
a
monohydric alcohol, but polyhydric alcohol is also suitable. The alcohol is
can be a
monohydric alcohol of the formula R4OH, where R4 is straight-chain or
branched, cyclic or
branched cyclic alkyl of 1 to 16, alternatively 6 to 16, carbon atoms.
[0042] Specific, non-limiting examples of the alcohol include methanol,
ethanol, n-propanol,
isopropanol, cyclopropylcarbinol, n-butanol, sec-butanol, isobutanol, tert-
butanol, 2-
hydroxymethylfuran, amyl alcohol, isoamyl alcohol, vinylcarbinol,
cyclohexanol, n-hexanol,
4-methyl-2-pentanol, 2-ethylbutyl alcohol, sec-capryl alcohol, 2-ethylhexanol,
n-decanol,
lauryl alcohol, isocetyl alcohol and mixtures thereof In one embodiment, the
alcohol is 2-
ethylhexanol. Additional specific, non-limiting examples of the alcohol
include phenol,
naphthol, (o,p)-alkylphenols, e.g. di-tert-butylphenol, and salicylic acid.
[0043] The molar ratio of the polyisobutenylsuccinic anhydride to the alcohol
can vary. It is
not necessary to use stoichiometric amounts of the alcohol, and even
comparatively small
molar amounts of the alcohol can be sufficient to form the
polyisobutenylsuccinimide. A
example molar ratio of the polyisobutenylsuccinic anhydride to alcohol is from
10 to 0.5,
alternatively from 4 to 0.8.
[0044] In this embodiment, the polyisobutenylsuccinic anhydride can be first
reacted with the
alcohol, then reacted with the first amine to form the
polyisobutenylsuccinimide. More
specifically, the polyisobutenylsuccinic anhydride can be first reacted with
the alcohol to
form a second reaction intermediate comprising a monoester of
polyisobutenylsuccinic acid,
which is then reacted with the first amine. In this embodiment, the
polyisobutenylsuccinic
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anhydride and the alcohol are combined in a reaction vessel.
After the
polyisobutenylsuccinic anhydride and the alcohol react, the first amine can be
introduced into
the reaction vessel. After the reaction, any alcohol, which is either
unreacted or cleaved, can
be removed in a conventional manner.
[0045] In an embodiment, the second reaction intermediate includes the
reaction product of
(1) the first reactive polyisobutene having a molecular weight Mn of from 500
to 5,000 g/mol
and a content of terminal double bonds of greater than 50, alternatively
greater than 70, mol
%, (2) maleic anhydride, and (3) the alcohol selected from the group
consisting of
monohydric alcohols of the formula R4OH, where R4 is straight-chain or
branched, cyclic or
branched cyclic alkyl of 1 to 16 carbon atoms.
[0046] The second reaction intermediate which is formed during the formation
of the
polyisobutenylsuccinimide can, if desired, also be isolated. The reaction
intermediate is not
only useful in the formation of the polyalkenylsuccinimide (A) but, alone or
in combination
with other additives, can also be used as additives for fuels or lubricants.
[0047] Alternatively in this embodiment, isolation of the second reaction
intermediate is not
necessary. That is, the polyisobutenylsuccinic anhydride, the first amine and
the alcohol are
reacted simultaneously, i.e., in a single step to from the
polyisobutenylsuccinimide. After the
reaction, any alcohol, which is either unreacted or cleaved, can be removed in
a conventional
manner.
[0048] In another embodiment, the polyalkenylsuccinimide (A) can be the
reaction product
of (1) the first reactive polyisobutene having a molecular weight (Mn) of from
500 to 5,000
g/mol and a content of terminal double bonds of greater than 50, alternatively
greater than 75,
mol %, (2) maleic anhydride, and (3) the first amine (A.2) having the formula:
H2N(CH2)õ-NH-[(CH2)y-NFI],-(CH2),NH2
where x and y are each independently an integer from 1 to 5, alternatively
from 2 to 4, and z
is an integer from 0 to 8, or mixtures thereof.
[0049] In another embodiment, the polyalkenylsuccinimide (A) includes the
reaction product
of (1) the first reactive polyisobutene having a number average molecular=
weight (Mn) of
= from 500 to 5,000 g/mol and a content of terminal double bonds of greater
than 50,
alternatively greater than 70, mol %, (2) maleic anhydride, and (3) a linear,
branched, cyclic
or cyclic branched alkylenepolyamine having 1 to 10, alternatively 2 to 4,
carbon atoms in
each alkylene group and 1 to 12, alternatively 2 to 12, alternatively 2 to 9,
alternatively 3 to
9, nitrogen atoms, of which at least one nitrogen atom is present as a primary
amino group, or
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mixtures thereof, including less than 30% by weight, based on the total weight
of the product,
of the corresponding polyisobutenylsuccinamide.
[0050] In another embodiment, the polyalkenylsuccinimide (A) includes the
reaction product
of the reaction intermediate (A.1), e.g. polyisobutenylsuccinic anhydride, and
the
nucleophilic reactant (A.2) comprising a C2 to C40, alternatively C2 to C20,
alternatively C2 to
C12 polyalkylene polyamine which includes from 2 to 12, alternatively 2 to 9,
alternatively 3
to 9, nitrogen atoms per molecule an amine. To form the polyalkenylsuccinimide
(A), e.g.
polyisobutenylsuccinimide, of this embodiment, 0.1 to 3.0, alternatively 0.2
to 1.0,
alternatively 0.2 to 0.6, mol of succinic moieties are reacted per equivalent
of the
nucleophilic reactant (A.2), e.g. amine, to form the polyalkenylsuccinimide
(A).
[0051] In some embodiments, the polyalkenylsuccinimide (A) has the following
structure:
o
NH
o NHN_NH
¨m
NH2
wherein m is an integer of from 2 to 80, alternatively from 2 to 40,
alternatively from 2 to 20,
alternatively from 6 to 16.
[0052] In some embodiments, the polyalkenylsuccinimide (A) of the subject
disclosure
includes a minimal amount of corresponding amides (polyisobutenylsuccinimide
or
polyisobutenylsuccinic acid monoamide). More specifically, the
polyalkenylsuccinimide (A)
can include less than 30, alternatively less than 25, alternatively less than
20, alternatively
less than 15, % by weight corresponding amides, based on the total weight of
the
polyalkenylsuccinimide (A), of the corresponding amides.
In addition, the
polyalkenylsuccinimide (A) can include no ester fractions, even when the
polyalkenylsuccinimide (A) includes the reaction product of the reaction
intermediate (A.1),
the nucleophilic reactant (A.2), and the alcohol (A.3) and the reaction with
the alcohol (A.3)
is carried out in an intermediate stage.
Increased purity (minimal corresponding
amides/amide bi-products and lack of ester fractions) of the
polyalkenylsuccinimide (A) can
be attributed to the process by which the polyalkenylsuccinimide (A) is
formed.
[0053] In some embodiments the polyalkenylsuccinimide (A) has a number average
molecular weight (M) of greater than 500, alternatively greater than 800,
alternatively
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greater than 1,000, alternatively from 500 to 5,000, alternatively from 750 to
5,000,
alternatively from 1,000 to 4,000, alternatively from 1,000 to 3,000, g/mol.
The higher
molecular weight (e.g. M,, >1,000 g/mol) polyalkenylsuccinimide (A) reduces
fuel
consumption in internal combustion engines when added to the fuel combusted.
That is, the
polyalkenylsuccinimide (A) is an effective fuel economy additive. In contrast,
it is thought
that lower molecular weight (e.g. Mn 300 to 500 g/mol) molecules do not reduce
fuel
consumption in internal combustion engines when added to the fuel combusted.
IN some
embodiments, a hydrophobic moiety of such molecules known in the art is
typically derived
from synthetic or natural mono or oligo fatty acids with a chain length of
typically Cl2 to C20.
In contrast, polyalkenylsuccinimide (A), as is described above, can be formed
from the first
reactive polyisobutene having a chain length of C40 to C400, alternatively
from C40 to C200 and
a number average molecular weight (Mn) of from 500 to 5,000 g/mol.
[0054] The compositions can be added to fuel in an amount such that the
polyalkenylsuccinimide (A) can be present in the fuel in an amount of from 10
to 500,
alternatively from 20 to 200, alternatively from 25 to 75, mg/kg of fuel.
Further, the
polyalkenylsuccinimide (A) can be present in the compositions in an amount of
from 1 to 75,
alternatively 1 to 50, alternatively 5 to 40, alternatively 4 to 40,
alternatively 6 to 45,
alternatively 2 to 20, alternatively 4 to 15, alternatively from 5 to 12,
alternatively from 15 to
45, alternatively from 20 to 35, parts by weight per 100 parts by weight of
the composition.
The Polyisobutene Amine (B)
[0055] Referring back, in some embodiments, the compositions also include the
polyisobutene amine (B). The polyisobutene amine (B) as described herein
includes mono
and polyfunctional polyisobutene amines. In some embodiments, the
polyisobutene amine
(B) includes the reaction product of (B.1) a second polyolefin and (B.2) a
second amine.
The Second Polyolefin (B.1)
[0056] The second polyolefin (B.1) of the subject disclosure includes C2 to
C18, alternatively
C2 to CIO, alternatively C2 to C5, Olefin units. Non-limiting examples of
olefin units include
ethylene, propylene, butylene, isobutylene, pentene, octene-1, and styrene. In
some
embodiments, the second polyolefin (B.1) is a polyalkene. The second
polyolefin (B.1) can
be homopolymer, such as polyisobutylene, or copolymer of two or more of
different olefin
units. Non-limiting examples of copolymers which can be used to form the
second
polyolefin (B.1) include ethylene and propylene, butylene and isobutylene,
propylene and
isobutylene. Additional non-limiting examples of copolymers include copolymers
that
include a minor molar amount of olefin units, e.g. 1 to 10 mol %, are C4 to
C18 non-
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conjugated diolefin units such as a copolymer of isobutylene and butadiene or
a copolymer of
ethylene, propylene, and 1,4-hexadiene.
[0057] The second polyolefin (B.1) can be linear or branched. In some
embodiments, the
second polyolefin (B.1) has a number average molecular weight (Mn) of from 500
to 5,000,
alternatively from 750 to 4,000, alternatively from 1,000 to 3,000,
alternatively from 1,000 to
2,000, g/mol.
[0058] In some embodiments, the second polyolefin (B.1) is unsaturated. In a
some
embodiments, the second polyolefin (B.1) includes a terminal double bond.
[0059] To this end, in one embodiment, the second polyolefin (B.1) is a second
reactive
polyisobutene. The second reactive polyisobutene can be a highly reactive
polyisobutene
which has a high content of terminal ethylenic double bonds. In some
embodiments, the
second reactive polyisobutene has a content of terminal double bonds of
greater than 50,
alternatively greater than 70, alternatively greater than 75, alternatively
greater than 80,
alternatively greater than 85, mol %. The second reactive polyisobutene can
have a uniform
polymer backbone which includes greater than 85, alternatively greater than
90, alternatively
greater than 95, % by weight of isobutene units.
[0060] In some embodiments, the second reactive polyisobutene has a number
average
molecular weight (Mn) of from 500 to 5,000, alternatively from 750 to 4,000,
alternatively
from 1,000 to 3,000, alternatively from 1,000 to 2,000, g/mol. The dispersity
D (Mw/Mn),
i.e., the quotient of the weight average molecular weight Mw divided Mn, of
the second
reactive polyisobutene is less than 7, alternatively from 1.05 to 7. In one
embodiment, the
dispersity D (Mw/Mn) of the second reactive polyisobutene is less than 3. In
some
embodiments, a second reactive polyisobutene has a dispersity of less than 2.0
for Mr, less
than or equal to 2,000, and a dispersity of less than 1.5 for M,, less than or
equal to 1,000. In
some embodiments, the second reactive polyisobutene is free of organic and
inorganic bases,
water, alcohols, ethers, acids and peroxides.
[0061] Suitable non-limiting examples of the second reactive polyisobutene are
commercially available from BASF SE under the GLISSOPAL brand of
polyisobutenes.
The Second Amine (B.2)
[0062] As described above, the second polyolefin (B.1) reacts with the second
amine (B.2) to
form the polyisobutene amine (B). In some embodiments, the second amine (B.2)
has the
following formula:
HNRIR2
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wherein RI and R2 are each independently H, a C1-C18-alkyl, C2-C18-alkenyl, C4-
C18-
cycloalkyl, Ci-C18-alkylaryl, hydroxy-CI-C] 8-alkyl, poly(oxyalkyl),
polyalkylene polyamine,
a polyalkylene amine radical, a polyalkylene imine radical; or, together with
the nitrogen
atom to which they are bonded, form a heterocyclic ring.
[0063] Non-limiting examples of CI-C18-alkyl radicals include straight-chain
or branched
radicals having from 1 to 18 carbon atoms such as methyl, ethyl, iso- or n-
propyl, n-, iso-,
sec- or tert-butyl, n- or isopentyl; and also n-hexyl, n-heptyl, n-octyl, n-
nonyl, n-decyl, n-
undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl and n-
octadecyl, and also the
mono- or polybranched analogs thereof; and also corresponding radicals in
which the
hydrocarbon chain has one or more ether bridges.
[0064] Non-limiting examples of C2-C18-alkenyl radicals include the mono- or
polyunsaturated, alternatively mono- or diunsaturated analogs of the above-
mentioned alkyl
radicals having from 2 to 18 carbon atoms, in which the double bonds can be in
any position
in the hydrocarbon chain.
[0065] Non-limiting examples of Ca-C18-cycloalkyl radicals includes
cyclobutyl, cyclopentyl
and cyclohexyl, and also the analogs thereof substituted by from 1 to 3 C1-C4-
alkyl radicals;
the CI-Ca-alkyl radicals are, for example, selected from methyl, ethyl, iso-
or n-propyl, n-,
iso-, sec- or tert-butyl.
[0066] Non-limiting examples of Ci-C18-alkylaryl radicals include the Ci-C18-
alkyl group is
as defined above and the aryl group is derived from a monocyclic or bicyclic
fused or
nonfused 4- to 7-membered, in particular 6-membered aromatic or heteroaromatic
group such
as phenyl, pyridyl, naphthyl and biphenyl.
[0067] Non-limiting examples of C2-C18-alkenylaryl radicals include radicals
where the C2'
C18-alkenyl group is as defined above and the aryl group is as defined above.
Non-limiting
examples of hydroxy-C1-C18-alkyl radical include the analogs of the above CI-
C18-alkyl
radicals which have been mono- or polyhydroxylated, alternatively
monohydroxylated, in
particular monohydroxylated in the terminal position; for example 2-
hydroxyethyl and 3-
hydroxypropyl.
[0068] Non-limiting examples of a poly(oxyalkyl) radical, e.g. that can be
hydroxylated,
include radicals which are obtainable by alkoxylating the nitrogen atom with
from 2 to 10 C--
Ca-alkoxy groups in which individual carbon atoms can include hydroxyl groups.
Exemplary
alkoxy groups include methoxy, ethoxy and n-propoxy groups.
[0069] Non-limiting examples of a polyalkylene polyamine radical include
radicals of the
formula:
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Z-(NH-C1-C6-alkylene-NH),õ-Ci-C6-alkylene
where m is an integer from 0 to 5, Z is H or a C1-C6-alkyl. The Ci-C6-alkyl
represents
radicals such as methyl, ethyl, iso- or n-propyl, n-, iso-, sec- or tert-
butyl, n- or isopentyl, and
also n-hexyl, and C 1-C6-alkylene represents the corresponding bridged analogs
of these
radicals.
[0070] Non-limiting examples of the polyalkylene imine radical include
radicals comprising
from 1 to 10 CI-C4-alkylene imine groups, in particular ethylene imine groups.
Examples of
a heterocyclic ring include an optionally substituted 5- to 7-membered
heterocyclic ring
which is optionally substituted by from one to three CI-CI-alkyl radicals and
optionally bears
one further ring heteroatom such as 0 or N.
[0071] Non-limiting examples of compounds of the formula HNRIR2 include:
ammonia
primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine,
n-
butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine,
hexylamine,
cyclopentylamine and cyclohexylamine; and also primary amines of the formula
CH3-0-
C2H4-NH2, C2H5-0-C2H4-NH2, CH3-0-C3H6-NH2, C2H5-0-C3H-NH2, n -C4H9-0-C4H8-NH2,
HO-C21-14-NH2, HO-C3H6-NH2 and HO-C4H8-NH2; secondary amines, for example
dimethylamine, diethylamine, methylethylamine, di-n-propylamine,
diisopropylamine,
diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine,
dihexylamine,
dicyclopentylamine, dicyclohexylamine and diphenylamine; and also secondary
amines of
the formula (CH3-0-C2H4)2NH, (C2H5-0-C2H4)2NH, (CH3-0-C3H6)2NH, (C2H5-0-
C3H6)2NH, (n-C4H9-0-C4H8)2NH, (HO-C2H4)2NH, (HO-C3H6)2NH and (H0--C4H8)2NH;
heterocyclic amines such as pyrrolidine, piperidine, morpholine and
piperazine, and also their
substituted derivatives such as N-C1-C6-alkylpiperazines and
dimethylmorpholine.
polyamines, for example C1-C4-alkylenediamines, di-C1-C4-alkylenetriamines,
tri-C1-C4-
alkylenetetramines and higher analogs; polyethylene imines, alternatively
oligoethylene
imines, consisting of from 1 to 10, alternatively from 2 to 6 ethylene imine
units. Non-
limiting examples of polyamines and polyimines are n-propylenediamine, 1,4-
butanediamine,
1,6-hexanediamine, diethylenetriamine, triethylenetetramine and polyethylene
imines, and
also their alkylation products, for example 3-(dimethylamino)-n-propylamine,
N,N-
dimethylethylenediamine, N,N-diethylethylenediamine = and
N,N,N',N'-
tetramethyldiethylenetriamine. Ethylenediamine is yet another non-limiting
example.
The Polyisobutene Amine (B)
[0072] The the mono or polyfunctional polyisobutene amine (B) can be formed
via various
reactions under various reaction conditions.
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[0073] For example, in one embodiment, the mono or polyfunctional
polyisobutene amine
(B) includes the reaction product of a halogenated hydrocarbon, e.g.
halogenated
polyisobutene, and the second amine described above. More specifically, the
halogen atoms
of the hydrocarbon chain are replaced by a polyamine group, while a hydrogen
halide is
formed. The hydrogen halide can then be removed in any suitable way, for
example, as a salt
with excess polyamine. The reaction between halogenated hydrocarbon and the
second amine
can be effected at elevated temperature in the presence of a solvent, e.g. a
solvent having a
boiling point of at least 160 C.
[0074] As another example, the polyisobutene amine (B) can be formed via
alkylation of
aliphatic polyamines. For example, the second amine, e.g. a polyamine, can be
reacted with
an alkyl or alkenyl halide. The formation of the alkylated polyamine is
accompanied by the
formation of hydrogen halide, which is removed, for example, as a salt of the
starting
polyamine which is present in excess.
[0075] As yet another example, a polyalkene having a terminal double bond
whose beta
carbon atoms carries a methyl group, e.g. the second reactive polyisobutene,
can be
chlorinated with a theoretical quantity of chlorine to yield an alpha-
polyisobutyl allyl chloride
and beta-polyisobutyl methyallyl chloride, while hydrochloric acid is split
off. During
chlorination, side reactions also produce a quantity of dichloro compound. The
second
amine, e.g. a polyamine, is then alkylated with the chlorination compounds
obtained to form
polyisobutene amine (B). For example, the first reactive polyisobutylene is
treated with
chlorine in an inert solvent at room temperature and the resulting
polyisobutenyl chloride is
converted with tetraethylenepentamine into
monoisobuitenyltetraethyleliepentamine or
di isobutenyltetraethylenepentamine.
[0076] In another embodiment, the polyisobutene amine (B) includes the
reaction product of
the second reactive polyisobutene, a second amine having the following
formula;
HNR2R3
wherein R2 and R3 are each independently H, a C1-C18-alkyl, C2-C18-alkenyl, C4-
C18-
cycloalkyl, C1-C18-alkylaryl, hydroxy-CI-C18-alkyl, poly(oxyalkyl),
polyalkylene polyamine
or a polyalkylene amine radical; or, together with the nitrogen atom to which
they are
bonded, form a heterocyclic ring.
[0077] For example, the mono or polyfunctional polyisobutene amine (B)
includes a reaction
product formed via hydroformylation of the second reactive polyisobutene to
form an oxo
intermediate and subsequent reductive amination of the oxo intermediate in the
presence of
ammonia.
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[0078] Specifically, the polyisobutene amine (B) can be formed via
hydroformylation of an
appropriate polyalkene, e.g. the second reactive polyisobutene, with a rhodium
or cobalt
catalyst in the presence of CO and 112 at a temperature of from 80 to 200 . C
and CO/H2
pressures of up to 600 bar and then subjecting the oxo product to a Mannich
reaction or
amination under hydrogenating conditions. The amination reaction can be
carried out at 80
to 200 C and pressures of equal to or less than 600, alternatively from 80 to
300, bar.
[0079] In this formation process, it is advantageous to use a suitable, inert
solvent in order to
reduce the viscosity of the reaction mixture. Non-limiting examples of such
solvents include
aliphatic, cycloaliphatic, and aromatic hydrocarbons having low sulfur
content. In one
embodiment, an aliphatic solvent which is free of sulfur compounds and include
less than 1%
of aromatics is used. Such solvents have the advantage that, at high amination
temperatures,
no heat of hydrogenation is liberated and no hydrogen is consumed. In the
amination and
hydroformulation reaction, the solvent content can be from 0 to 70 % by
weight, depending
on the viscosity of the polymer and of the solvent.
[0080] In this formation process, polybutene conversions of =80 to 90 % can
readily be
achieved. In one embodiment, the second reactive polybutene comprising equal
to or greater
than 80 % by weight isobutene and having a number average molecular weight
(Mn) of from
300 to 5000, alternatively from 500 to 2500, g/mol is used. In this
embodiment, the second
reactive polybutene has a mean degree of polymerization P of from 10 to 100
and a content E
of double bonds which are capable of reacting with maleic anhydride is from 60
to 90 %. A
value E of 100% corresponds to the calculated theoretical value where each
molecule of the
butene or isobutene polymer includes one reactive double bond of this type.
The value is
calculated for a reaction of polyisobutene with maleic anhydride in a weight
ratio of 5:1, the
stirred mixture being heated for 4 hours at 200 C.
[0081] Independent of how the polyisobutene amine (B) is formed, the
polyisobutene amine
(B) of the compositions has excellent low temperature properties, e.g. a low
cloud point, a
low pour point, and is stable when stored at low temperatures. Further, the
polyisobutene
amine (B) can function as a detergent in internal combustion engines when
added to the fuel
combusted.
[0082] To this end, the compositions can be added to fuel in an amount such
that the
polyisobutene amine (B) can be present in the fuel in an amount of from 20 to
2,000,
alternatively from 50 to 1,000, alternatively from 100 to 500, mg/kg of fuel.
Further, the
polyisobutene amine (B) can be present in the compositions in an amount of
from 5 to 70,
alternatively from 10 to 60, alternatively from 10 to 40, alternatively from
30 to 60,
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alternatively from 5 to 35, alternatively from 15 to 25, parts by weight per
100 parts by
weight of the composition.
The Carrier Oil (C)
100831 Referring back, the compositions also include the carrier oil (C). One
or more
different carrier oils can be added to the compositions, i.e., the carrier oil
(C) can include a
mixture of one or more different types of carrier oil. The carrier oil (C) can
include mineral
carrier oil, synthetic carrier oil, and combinations thereof. The carrier oil
(C) can include one
or more different carrier oils selected from the group of mineral oils,
polyethers,
polyetheramines, and esters. The compositions can include any carrier oil
known in the art,
including those carrier oils not specifically described herein.
100841 As is set forth above, the compositions can include one or more mineral
carrier oils.
Non-limiting examples of mineral carrier oils include fractions obtained in
mineral oil
processing, such as kerosine or naphtha, or brightstock or base oils. Non-
limiting examples
of suitable mineral carrier oils include naphthenic or paraffinic mineral oils
having a viscosity
of from 2 to 25 mm2/s at 100 C.
[0085] As is set forth above, the compositions can include one or more
polyether carrier oils.
Non-limiting examples of polyether carrier oils include polyalkylene oxides
having a number
average molecular weight (Mn) of equal to or greater than 500 g/mol and
propoxylates.
Generally, the polyalkylene oxide carrier oils are formed by polymerizing one
or more
alkylene oxides, such as ethylene oxide (EO), propylene oxide (PO), and/or
butylene oxide
(BO) with an initiator in the presence of a catalyst. The initiator used to
form the
polyalkylene oxide can be an alkanol, an alkanediol, an amine, or an
alkylphenol. For
example, the initiator can be 1,6-hexanediol, 1,8-octanediol, 2-ethylhexanol,
2-
propylhexanol, isotridecanol, isononylphenol, isodecylphenol, and/or
isotridecylamine. The
polyalkylene oxides can be linear or branched and can have a random,
repeating, or block
structure. One non-limiting example of a suitable polyether carrier oil is a
polyalkylene
oxide formed from 50, alternatively from 8 to 30, mol of propylene oxide or
butylene oxide
or of a mixture thereof, per initiator molecule. Another non-limiting example
of a suitable
polyether carrier oil is a propoxylate having the following formula:
R440-CH2-CH(CH3)b-0H
wherein n is an integer of from 14 to 17, and R4 is straight-chain or branched
C8-C18-alkyl or
C8-C18-alkenyl
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[0086] As is set forth above, the compositions can include one or more
polyetheramine
carrier oils. Non-limiting examples of polyetheramine carrier oils include
polyetheramines
based on EO, PO, and/or BO and ammonia or primary or secondary mono- or
polyamines
having a number average molecular weight (Mn) of equal to or greater than 500
g/mol. Such
polyetheramines can be prepared from polyethers by an amination reaction
wherein the
terminal hydroxyl group is replaced by an amino group with elimination of
water.
[0087] As is set forth above, the compositions can include one or more esters
of mono- or
polycarboxylic acids with alkanols or polyols carrier oils. Non-limiting
examples of such
ester carrier oils include esters of mono- or polycarboxylic acids with
alkanols or polyols
having a minimum viscosity of 2 mm2/s at 100 C, aliphatic or aromatic mono- or
polycarboxylic acids, and C6 to C24 ester alcohols or ester polyols, adipates,
phthalates,
isophthalates, terephthalates, and trimellitates of isooctanol, isononanol,
isodecanol and of
isotridecanol.
[0088] In some embodiments, the compositions include a propoxylate carrier oil
having the
following formula:
R440-CH2-CH(CH3)Jn-OH
wherein n is an integer of from 8 to 35, alternatively from 14 to 17, and R4is
straight-chain or
branched C8-C18-alkyl or C8-C18-alkenyl.
[0089] In one embodiment, R4 is straight-chain or branched alkyl of 10 to 16
carbon atoms,
or mixtures thereof In another embodiment, R4 is alkyl of 12 to 14 carbon
atoms or is a
mixture of such alkyl radicals. In yet another embodiment, R4 has 13 carbon
atoms.
[0090] In one embodiment, n is an integer from 12 to 18. In another
embodiment, n is an
integer from 14 to 17. In yet another embodiment, n is an integer from 14 to
16. In still yet
another embodiment, n is 15. Of course, the above numerical data for n is an
average value
since many preparation methods produce a mixture of compounds with varying
molecular
weight distribution.
[0091] In one embodiment, the propoxylate carrier oil has the formula above
wherein n is an
integer from 14 to 16, alternatively 15, and R4 is a branched C13-alcohol, in
particular C13-
monoalcohol. Branched C13-alcohols can be obtainable by oligomerization of C2-
C6-olefins,
in particular C3- or C4-olefins, and subsequent hydroformylation.
=
[0092] The propoxylate carrier oil of this embodiment is prepared by reacting
an alcohol, as
an initiator molecule, with propylene oxide in the presence of an alkali, e.g.
sodium
hydroxide solution, potassium hydroxide solution, sodium methylate, potassium
methylate, or
another alkali metal alkoxide, at from 120 to 160, alternatively from 130 to
160, C, to give
CA 02912513 2015-11-13
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the desired adducts. After alkoxylation is complete, the propoxylate carrier
oil is freed from
the catalyst, for example by treatment with magnesium silicate. In one
embodiment, the
propoxylate carrier oil is propoxylated isotridecanol.
[0093] In a another embodiment, the compositions include a dialkylphenol-
initiated
propoxylate carrier oil having the following formula:
R6
R7
ri 5
q
R7
where R5 and R6 independently of one another are each branched or straight-
chain C6 to C30
alkyl groups, one of the two radicals R7 is methyl and the other is hydrogen
and q is from 1 to
100. This embodiment can also include a monoalkylphenol-initiated propoxylate
carrier oil,
this propoxylate carrier oil represented by the formula above with the proviso
that R6 is
omitted.
[0094] In general, any mixture of the carrier oils described above can be
included in the
carrier oil (C) of the compositions. To this end, in another embodiment, the
carrier oil (C)
includes a mixture of polyether carrier oil and ester carrier oil.
[0095] Suitable polyether carrier oils include polyalkylene oxides having a
number average
molecular weight (M) of equal to or greater than 500 g/mol. The polyalkylene
oxides of this
embodiment can be formed from initiators such as aliphatic and aromatic mono-,
di- or
polyalcohols or even amines or amides and alkylphenols. The polyalkylene
oxides of this
embodiment can be formed from alkylene oxides such as ethylene oxide EO, PO,
and BO,
but it is also possible to use higher oxides for forming these polyalkylene
oxides.
[0096] Suitable esters carrier oils include esters of aliphatic or aromatic
mono- or
polycarboxylic acids with long-chain alcohols, polyol esters (based for
example on neopentyl
glycol, pentaerythritol or trimethylolpropane with corresponding
monocarboxylic acids) and
oligomer or polymer esters, for example those based on dicarboxylic acid, a
polyol and a
monoalcohol, and esters of aromatic di-, tri- and tetracarboxylic acids with
long-chain
aliphatic alcohols composed solely of carbon, hydrogen and oxygen, the total
number of
carbon atoms of the esters being 22 or more and the molecular weight being
from 370 to
1500, alternatively from 414 to 1200, g/mol. Suitable esters can have a
minimum viscosity of
2 mm2/s at 100 C. In one embodiment, the ester is an adipate, phthalate,
isophthalate,
terephthalate and trimellitate of isooctanol, isononanol, isodecanol and
isotridecanol, and
combinations thereof.
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[0097] The carrier oil (C) functions to carry the components ((A), (B), etc.)
of the
compositions and can also function to reduce deposits in the region of the
intake valves of an
engine. To this end, the compositions can be added to fuel in an amount such
that the carrier
oil (C) is typically added to the fuel in an amount of from 10 to 2,000,
alternatively, from 20
to 1,000, alternatively from 50 to 500, mg/kg of fuel. Further, the carrier
oil (C) can be
present in the compositions in an amount of from 2 to 94, alternatively from 2
to 80,
alternatively from 5 to 60, alternatively from 10 to 30, alternatively from 12
to 18,
alternatively from 5 to 15, alternatively from 2 to 20, parts by weight per
100 parts by weight
of the composition.
Additives
[0098] The compositions can include one or more additives, differing from
components (A)
and (B) and (C) described above, selected from the group of detergents,
lubricity additives,
corrosion inhibitors, antioxidants, demulsifiers, metal deactivators,
dehazers, markers,
solvents, cetane number improvers, antifoams, solubilizers, deodorants,
dehazers, and other
additives. The compositions can include, but do not require solubilizers.
Solubilizers are
materials, known in the art, which improve miscibility of the components
included in the fuel
additive compositions and thus improve the homogeneity of the fuel additive
compositions.
Detergents
[0099] One or more detergents, differing from components (A) and (B) described
above, can
be added to the compositions. Suitable examples include detergents, other than
the
polyisobutene amine (B), which have detergent action and/or have valve seat
wear-inhibiting
action. Suitable, non-limiting examples of the one or more detergents include
neutral metal
sulphonates, phenates and salicylates, and combinations thereof, which are
described below.
[00100] One suitable detergent is a compound having at least one
hydrophobic
hydrocarbon radical having a number average molecular weight (Mn) of from 85
to 20,000
and at least one polar moiety selected from: (a) mono- or polyamino groups
having up to 6
nitrogen atoms, of which at least one nitrogen atom has basic properties; (b)
nitro groups
which can be in combination with hydroxyl groups; (c) hydroxyl groups in
combination with
mono- or polyamino groups, in which at least one nitrogen atom has basic
properties; (d)
carboxyl groups or their alkali metal or their alkaline earth metal salts; (e)
sulfonic acid
groups or their alkali metal or alkaline earth metal salts; (0 polyoxy-C2- to -
C4-alkylene
groups which are terminated by hydroxyl groups, mono- or polyamino groups, in
which at
least one nitrogen atom has basic properties, or by carbamate groups; (g)
carboxylic ester
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groups; and/or (h) moieties obtained by Mannich reaction of substituted
phenols with
aldehydes and mono- or polyamines.
[00101]
The hydrophobic hydrocarbon radical in the aforementioned detergents that
improves the solubility of the compositions in the fuel can have a number
average molecular
weight (M) of from 85 to 20,000, alternatively from 113 to 5,000,
alternatively from 300 to
5,000. Example hydrophobic hydrocarbon radicals, especially in conjunction
with the polar
moieties (a), (c), (h) and (i), include polypropenyl, polybutenyl and
polyisobutenyl radical
each having number average molecular weight (M) of from 300 to 5,000,
alternatively from
500 to 2,500, alternatively from 700 to 2,300, g/mol.
[00102]
Detergents comprising mono- or polyamino groups (a) can be
polyalkenemono- or polyalkenepolyamines based on polypropene or conventional,
i.e.,
having predominantly internal double bonds, polybutene or polyisobutene having
number
average molecular weight (Mn) from 300 to 5,000. When polybutene or
polyisobutene
having predominantly internal double bonds (usually in the beta and gamma
position) are
used as starting materials in the preparation of the detergents, a possible
preparative route is
by chlorination and subsequent amination or by oxidation of the double bond
with air or
ozone to give the carbonyl or carboxyl compound and subsequent amination under
reductive
(hydrogenating) conditions. The amines used for the amination can be, for
example,
ammonia, monoamines or polyamines, such as dimethylaminopropylamine,
ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
[00103]
Detergents comprising monoamino groups (a) can also be the hydrogenation
products of the reaction products of polyisobutenes having an average degree
of
polymerization P of from 5 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and
oxygen. Detergents comprising monoamino groups (a) can also be compounds
obtainable
from polyisobutene epoxides by reaction with amines and subsequent dehydration
and
reduction of the amino alcohols.
[00104]
Detergents comprising nitro groups (b) which can be in combination with
hydroxyl groups, can be reaction products of polyisobutenes having an average
degree of
polymerization P of from 5 to 100 or from 10 to 100 with nitrogen oxides or
mixtures of
nitrogen oxides and oxygen. These reaction products are generally mixtures of
pure
nitropolyisobutenes (e.g. alpha,beta-dinitropolyisobutene)
and mixed
hydroxynitropolyisobutenes (e.g. alpha-nitro-beta-hydroxypolyisobutene).
[00105]
Detergents comprising hydroxyl groups in combination with mono- or
polyamino groups (c) can be reaction products of polyisobutene epoxides
obtainable from
23
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polyisobutene having terminal double bonds and number average molecular weight
(Mn)
from 300 to 5,000, with ammonia or mono- or polyamines.
[00106]
Detergents comprising carboxyl groups or their alkali metal or alkaline earth
metal salts (d) can be copolymers of C2 to C40 olefins with maleic anhydride
which have a
total molar mass of from 500 to 20,000 and of whose carboxyl groups some or
all have been
converted to the alkali metal or alkaline earth metal salts and any remainder
of the carboxyl
groups has been reacted with alcohols or amines. Such detergents can prevent
valve seat
wear and can be used in combination with the polyisobutene amine (B).
[00107]
Detergents comprising sulfonic acid groups or their alkali metal or alkaline
earth metal salts (e) can be alkali metal or alkaline earth metal salts of an
alkyl
sulfosuccinate.
Such detergents also can prevent valve seat wear and can be used in
combination with the polyisobutene amine (B).
[00108]
Detergents comprising polyoxy-C2-C4-alkylene moieties (0 can be polyethers
or polyether amines which are obtainable by reaction of C2- to C60-alkanols,
C6- to C30-
alkanediols, mono- or di-C2-C30-alkylamines, C1-C30-alkylcyclohexanols or CI-
Cm-
alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide
and/or butylene
oxide per hydroxyl group or amino group and, in the case of the polyether
amines, by
subsequent reductive amination with ammonia, monoamines or polyamines. In the
case of
polyethers, such products can also have carrier oil properties. Examples of
these detergents
include tridecanol butoxylates, isotridecanol butoxylates, isononylphenol
butoxylates and
polyisobutenol butoxylates and propoxylates and also the corresponding
reaction products
with ammonia.
[00109]
Detergents comprising carboxylic ester groups (g) can be esters of mono-, di-
or tricarboxylic acids with long-chain alkanols or polyols, in particular
those having a
minimum viscosity of 2 mm2/s at 100 C. The mono-, di- or tricarboxylic acids
used can be
aliphatic or aromatic acids, and particularly suitable ester alcohols or ester
polyols are long-
chain representatives having, for example, from 6 to 24 carbon atoms. Example
esters
include adipates, phthalates, isophthalates, terephthalates and trimellitates
of isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products can also have
carrier oil
properties.
[00110]
Detergents comprising moieties obtained by Mannich reaction of substituted
phenols with aldehydes and mono- or polyamines (h) can be reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or polyamines
such as
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ethylenediamine, diethyl enetriamine, triethylenetetramine,
tetraethylenepentamine or
dimethylaminopropylamine.
Lubricity Additives
[00111]
One or more lubricity additives can also be added to the compositions. Non-
limiting examples of lubricity additives include certain carboxylic acids or
fatty acids,
alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines, hydroxyacetoamides or
castor oil.
The aforementioned carboxylic acids or fatty acids can be present as monomer
and/or dimeric
species.
Corrosion Inhibitors
[00112]
One or more corrosion inhibitors can also be included in the compositions.
Non-limiting examples of corrosion inhibitors include ammonium salts of
organic carboxylic
acids, which tend to form films. Heterocyclic aromatics can also be included
as corrosion
inhibitors for nonferrous metals. Amines for reducing the pH can also be
included with
corrosion inhibitors.
Antioxidants
[00113]
One or more antioxidants or stabilizers can also be included in the
compositions. Non-limiting examples of antioxidants or stabilizers include
amines, such as
para-phenylenediamine, dicyclohexylamine, morpholine or derivatives of these
amines,
phenolic antioxidants, such as 2,4-di-tert-butylphenol or 3,5-di-tert-buty1-4-
hydroxyphenyl-
propionic acid and derivatives thereof.
[00114]
Non-limiting examples of antioxidants include alkylated monophenols, for
example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl -4,6-dimethylphenol,
2,6-di-tert-buty1-
4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-
isobutylphenol, 2,6-
dicyclopenty1-4-methylphenol, 2-(a-methy1cyc1ohexy1)-4,6-dimethy1phenol, 2,6-
dioctadecy1-
4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-
methoxymethylphenol, 2,6-di-
nony1-4-methylpheno 1, 2,4-dimethyl -6(1 '-methylundec- 1 '-yl)phenol, 2,4-
dimethy1-6-( 1 '-
methylheptadec- 1 '-yl)phenol, 2,4-dimethy1-6-(1 '-methyltridec- 1 '-
yl)phenol, and combinations
thereof.
[00115]
Other non-limiting examples of suitable antioxidants include
alkylthiomethylphenols, for example 2,4-dioctylthiomethy1-6-tert-butylphenol,
2,4-
dioctylthiomethy1-6-methylphenol, 2,4-dioctylthiomethy1-6-ethylphenol,
2,6-
didodecylthiomethy1-4-nonylphenol, and combinations thereof; hydroquinones and
alkylated
hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-
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butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-dipheny1-4-
octadecyloxyphenol, 2,6-
di-tert-butylhydroquinone, 2,5 -di-tert-butyl-4-hydroxyanisole, 3
,5 -di-tert-buty1-4-
hydroxyanisole, 3 ,5 -di-tert-butyl-4-hydroxyphenyl
stearate, bis-(3,5-di-tert-buty1-4-
hydroxyphenyl) adipate, and combinations thereof; hydroxylated thiodiphenyl
ethers, for
example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-
octylphenol), 4,4'-thiobis(6-
tert-buty1-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-
thiobis-(3,6-di-sec-
amylphenol), 4,4'-bis-(2,6-dimethy1-4-hydroxyphenyl) disulfide, and
combinations thereof;
alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-
methylphenol), 2,2'-
methylenebis(6-tert-buty1-4-ethylphenol),
2,2'-methylenebis [4-methy1-6-(a-
methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-
methylenebis(6-nony1-4-methylphenol), 2
,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-
ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-buty1-4-
isobutylphenol), 2,2'-
methylenebis [6-(a-methylbenzy1)-4-nonylphenol],
2,2'-methylenebis[6-(a,a-
dimethylbenzyl) -4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-
methylenebis(6-tert-buty1-2-methylphenol), 1 , 1 -bi s(5 -tert-butyl-4-hydr
oxy-2-
methylphenyl)butane, 2,6-bis(3-tert-buty1-5-methy1-2-hydroxybenzy1)-4-
methylphenol, 1,1,3 -
tri s(5 -tert-butyl-4-hydroxy -2-methylphenyl) butane, 1 ,1 -bis(5-tert-buty1-
4-hydroxy-2-
methyl-pheny1)-3 -n-dodecylmercapto butane, ethylene glycol bis[3,3-bis(3'-
tert-buty1-4'-
hydroxyphenyl)butyrate],
bis(3-tert-buty1-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis [2-(3'-tert-butyl -2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-
methylphenyl]terephthalate,
1 , 1 -bis-(3,5-dimethy1-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-buty1-4-
hydroxyphenyl)propane, 2,2-bis-(5-tert-buty1-4-hydroxy-2-methylphenyl) -
4-n-
dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-buty1-4-hydroxy-2-methyl
phenyl)pentane, and
combinations thereof can be utilized as antioxidants; 0-, N- and S-benzyl
compounds, for
example 3,5,3',5'-tetra-tert-buty1-4,4'-dihydroxydibenzyl ether, octadecy1-4-
hydroxy-3,5-
dimethylbenzylmercaptoacetate, tris-(3,5-di-tert-buty1-4-hydroxybenzypamine,
bis(4-tert-
buty1-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,
bis(3,5-di-tert-buty1-4-
hydroxybenzyl)sul fide, isoocty1-3,5di-tert-buty1-4-hydroxy
benzylmercaptoacetate, and
combinations thereof; hydroxybenzylated malonates, for example dioctadecy1-2,2-
bis-(3,5-di-
tert-buty1-2-hydroxybenzy1)-malonate,
di-octadecy1-2-(3-tert-buty1-4-hydroxy-5 -
methylbenzy1)-malonate,
di-dodecylmercaptoethy1-2,2-bis-(3,5-di-tert-buty1-4-
hydroxybenzyl)malonate, bis [4-(1 , 1 ,3 ,3 -tetramethylbutyl)pheny1]-2,2-
bis(3 ,5 -di-tert-buty1-4-
hydroxybenzyl)malonate, and combinations thereof; triazine compounds, for
example 2,4-
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bis(octylmercapto)-6-(3,5-di-tert-buty1-4-hydroxyani 1 ino)-1,3 ,5 -triazine,
2-octylmercapto-
4,6-bis(3,5-di-tert-buty1-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-
4,6-bis(3,5-di-
tert-buty1-4-hydroxyphenoxy) -1,3 ,5 -triazine, 2,4,6-tris(3 ,5 -di-tert-buty1-
4-hydroxyphenoxy)-
1,2,3 -triazine,
1,3 ,5-tris(3 ,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3 ,5-tris(4-
tert-
buty1-3 -hydroxy-2,6-dimethylbenzyl 2,4,6-tris(3,5-di-tert-buty1-4-
hydroxyphenylethyl)-1,3,5-
triazine, 1,3 ,5 -tris(3 ,5-di-tert-butyl-4-hydroxyphenyl propiony1)-hexahydro-
1,3,5-triazine,
1,3 ,5 -tris(3 ,5-dicyclohexy1-4-hydroxybenzyl)isocyanurate,
and combinations thereof;
aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-buty1-4-
hydroxybenzy1)-2,4,6-trimethylbenzene, 1,4 -bis(3 ,5 -di-tert-butyl-4-
hydroxybenzy1)-2,3 ,5,6-
tetramethylbenzene, 2,4,6-tris(3,5-di-tert-buty1-4-hydroxybenzyl)phenol, and
combinations
thereof; benzylphosphonates, for example
dimethy1-2,5-di-tert-buty1-4-
hydroxybenzylphosphonate,
diethyl-3 ,5 -di-tert-butyl-4 -hydroxybenzylpho sphonate,
dioctadecyl 3 ,5 -di-tert-butyl -4-hydroxybenzylphosphonate, dioctadecy1-5-
tert-buty1-4-
hydroxy 3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of
3,5-di-tert-
buty1-4-hydroxybenzylphosphonic acid, and combinations thereof
acylaminophenols, for
example 4-hydroxylauranilide, 4-hydroxystearanilide,
octyl N-(3 ,5 -di-tert-buty1-4-
hydroxyphenyl)carbamate; esters of [3-(3,5-di-tert-buty1-4-
hydroxyphenyl)propionic acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2 .2 .2]
octane, and
combinations thereof; esters of 13-(5-tert-buty1-4-hydroxy-3-
methylphenyppropionic acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol,
1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl -1-phospha-2,6,7-trioxabicyclo [2 .2
.2]octane, and
combinations thereof; esters of 13-(3,5-dicyclohexy1-4-hydroxyphenyl)propionic
acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-
hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol,
diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3 -thiaundecanol, 3 -thiapentade canol,
trimethylhexanediol,
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tri methyl olpropane, 4-
hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo [2 .2 .2] octane, and
combinations thereof; esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid
with mono- or
polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol,
1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol,
diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol,
trimethylolpropane, 4-hydroxym ethyl - 1 -phospha-2,6,7-trioxabicyclo [2 .2
.2] octane, and
combinations thereof; compounds including nitrogen, such as amides of 13-(3,5-
di-tert-buty1-
4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3 ,5 -di-tert-buty1-4-
hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3 , 5 -di-tert-butyl
-4-
hydroxyphenylpropionyl)trimethylenediamine,
N,N'-bis(3 ,5 -di-tert-buty1-4-
hydroxyphenylpropionyl)hydrazine; aminic compounds such as N,N'-diisopropyl-p-
phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis (1,4-
dimethylpenty1)-p-
phenylenediamine, N,N'-bis( 1 -ethyl-3 -methylpenty1)-p-phenylenediamine,
N,N'-bis( 1 -
methylhepty1)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-
diphenyl-
p-phenylenediamine, N,N-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-
phenyl-p-
phenylenediamine, N-(1 ,3 -dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-
methylhepty1)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-
phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-
phenylenediamine,
diphenylamine, N-allyldiphenylamine, 4-i sopropoxydiphenylamine, N-
phenyl- 1 -
naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-
tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol,
4-
nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-
methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino
methylphenol, 2,4'-
diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl -
4,4'-
diaminodiphenylmethane, 1 ,2-bis [(2-methyl-phenyl)amino] ethane,
1,2-
bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-
dimethylbutyl)phenyl]amine, tert-
octylated N-phenyl- 1-naphthylamine, a mixture of mono- and dialkylated tert-
butyl/tert-
octyldiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines,
mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-
dimethyl -4H-
1,4-benzothiazine, phenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl -
1,4-
diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethyl piperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-
one and 2,2,6,6-
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tetramethyl piperidin-4-ol, and combinations thereof; aliphatic or aromatic
phosphites, esters
of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or
dithiophosphoric
acid, 2,2,12,12-tetramethy1-5,9-dihydroxy-3,7,1trithiatridecane and 2,2,15,15-
tetramethy1-
5,12-dihydroxy-3,7,10,14-tetrathiahexadecane, and combinations thereof; and
sulfurized fatty
esters, sulfurized fats and sulfurized olefins, and combinations thereof.
Demulsifiers
[00116] One or more demulsifiers can also be included in the compositions.
Although
a single demulsifier can be included in the compositions, more than one
demulsifier is can be
included in the compositions. Each demulsifier can include one or more
solvents which
facilitate dispersion of the demulsifier in the compositions. As such, the one
or more
demulsifiers and one or more solvents included therewith are collectively
referred to herein
as (D) a demulsifier package. When added to the compositions, the demulsifier
package (D)
prevents the fuel, additivated with the compositions, from forming an emulsion
with water.
Specifically, when water and the additivated fuel are mixed, the demulsifier
package (D)
increases the rate at which water and additivated fuel separate into layers,
decreases the
amount of water in the fuel layer, decreases the amount of non-aqueous
components in the
water, and prevents the formation of an emulsion layer. The properties
imparted by the
demulsifier package (D) on the additivated fuel are collectively referred to
as the
demulsification properties of the demulsifier package (D).
[00117] ASTM Test Method D 1094 ¨ 07 and ExxonMobil Analytical Method AM-S
529-08 can be used to test the demulsification properties of the demulsifier
package (D). In
such tests, the compositions, including the demulsifier package (D), is mixed
with fuel to
form additivated fuel. In turn, the additivated fuel is mixed with water and
tested in
accordance with methods such as those set forth above to determine the extent
to which the
additivated fuel and water emulsify.
[00118] As is set forth in the background, fuel additive compositions
including
polyalkenylsuccinimides and other additives can phase separate over time,
especially at lower
temperatures (e.g. temperatures below 23 C). ExxonMobil Analytical Method FWI-
013 can
be used to test the storage stability (i.e. the homogeneity and resistance to
phase separation)
of the compositions. The compositions disclosed herein are homogenous and
resistant to
phase separation when stored "neat", i.e., not in additivated fuel. Although
demulsifiers can
provide demulsification properties to additivated fuel, demulsifiers can also
cause phase
separation of the compositions over time or upon exposure to lower
temperatures. The
demulsifier package (D) used with the compositions disclosed herein provides
the
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compositions with robust demulsification properties, and does not cause phase
separation of
the compositions during storage.
[00119] The demulsifier package (D) can include a demulsifier selected
from salts of
fatty acids, alkylamino carboxylic acids, organo sulfur compounds (e.g.
sulfonic acids,
alkylaryl sulfonate), polyetherols, and combinations thereof. The demulsifier
package (D)
can include any combination of demulsifiers selected from the chemical genera
set forth in
the previous sentence, and can include more than one chemical species from
each chemical
genus.
[00120] Polyetherols include the reaction product of a base molecule (also
known as an
initiator) and an alkylene oxide, in a chemical reaction known as
alkoxylation. The base
molecule is selected to impart certain physical properties to the polyetherol,
for example, a
base molecule including N or a cyclic hydrocarbon can be used to form the
polyetherol. The
alkylene oxide can be selected from the group of EO, PO, BO, and combinations
thereof.
Alkoxylation enables control of hydrophilic-lipophilic balance value ("HLB
value"), Mn, and
various other properties of the resulting polyetherol. Alkoxylation can be
carried out to form
polyetherols having a "block" structure (block polyetherols) and/or a "random"
structure. In
some embodiments, the polyetherol can have a heteric structure. For example,
the
polyetherol can have a totally heteric (or random) EO, PO structure. As
another example, the
polyetherol can have heteric, but uniform blocks, e.g. blocks comprising EO
and blocks
comprising PO. As yet another example, the polyetherol can have heteric blocks
and uniform
blocks, e.g. blocks comprising all EO and blocks comprising random EO, PO. As
such, the
base molecule and the type and amount of alkylene oxide used for alkoxylating
the base
molecule can be varied to achieve certain properties, such as calculated HLB
value and Mn,
which improve the demulsification properties the of the particular demulsifier
in the
compositions in additivated fuel.
[00121] The demulsifier package (D) can include a polyetherol demulsifier
selected
from alkoxylated butyl, amyl, and nonyl phenol resins, alkoxylated alkyl
phenol
formaldehyde resins, alkoxylated epoxy resins, alkoxylated polyethyleneimines,
oxyalklyated
alkyl phenols, amine alkoxylates, E0 polyetherols (e.g. nonylphenol
ethoxylate), PO
polyetherols, EO/PO block polyetherols, and combinations thereof. The
polyetherol can be a
block copolymer, a random copolymer, or a hybrid thereof. In one embodiment,
the
demulsifier package (D) includes a combination of the exemplary polyetherols
set forth
above.
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[00122]
As set forth above, the demulsifier package (D) can also include one or more
organo sulfur compounds. Specific, non-limiting examples of suitable organo
sulfur
compounds include sulfonic acids, alkylaryl sulfonates, and combinations
thereof. Specific,
non-limiting examples of suitable sulfonic acids include dodecyl benzene
sulfonic acid and
other alkylbenzene sulphonic acids. In one embodiment, the demulsifier package
(D)
includes a sulfonic acid.
[00123]
In some embodiments, the demulsifier package (D) includes less than 2,000,
alternatively less than 1,500, alternatively from 100 to 1,000, ppm of sulfur.
Accordingly,
in various embodiments, the demulsifier package (D), when used in the
compositions set
forth herein, delivers an amount of sulfur to fuel which is less than an
amount which can be
detected by instruments and test methods commonly used to detect sulfur
content in
additivated fuel.
[00124]
In one embodiment, the demulsifier package (D) is substantially free of
sulfur. "Substantially free" as used herein in relation to the demulsifier
package (D) being
substantially free of sulfur means that the demulsifier package (D) includes
sulfur containing
compounds in an amount less than about 25, alternatively less than about 10,
alternatively
less than 5, alternatively less than about 1, alternatively less than about
0.5, alternatively less
than about 0.2, alternatively less than about 0.15, alternatively 0 parts by
weight, based on
100 parts by weight of the .demulsifier package (D). Alternatively, in one
embodiment, the
demulsifier package (D) contributes less than 50, alternatively less than 25,
alternatively less
than 1.5, alternatively less than 1, alternatively less than 0.5,
alternatively less than 0.2,
alternatively less than 0.1, alternatively less than 0.05, alternatively less
than 0.01, mg of
sulfur/kg of fuel at the treat rates set forth herein.
[00125]
The compositions can be added to fuel in an amount such that the
demulsifier (or demulsifier package (D)) can be present in the fuel in an
amount of from 0.5
to 500, alternatively from 0.5 to 200, alternatively from 0.5 to 100,
alternatively from 0.5 to
50, alternatively from 1 to 25, mg/kg of fuel. Further, the demulsifier
package (D) can be
present in the compositions in an amount of less than 5, alternatively less
than 4, alternatively
less than 3, alternatively less than 2.5, alternatively less than 2,
alternatively less than 1.5,
alternatively less than 1, alternatively less than 0.8, alternatively from 0.1
to 5, alternatively
from 0.2 to 2.5, alternatively from 0.2 to 2, alternatively from 0.2 to 1,
alternatively from 0.2
to 2, alternatively from 0.2 to 0.8, parts by weight per 100 parts by weight
of the
composition.
Metal Deactivators
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[00126]
One or more metal deactivators can also be included in the compositions.
Non-limiting examples of the one or more metal deactivators include
benzotriazoles and
derivatives thereof, for example 4- or 5-alkylbenzotriazoles (e.g. triazole)
and derivatives
thereof, 4,5,6,7-tetrahydrobenzotriazole and 5,51-methylenebisbenzotriazole;
Mannich bases
of benzotriazole or triazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)triazole
and 1-[bis(2-
ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles such as 1-
(nonyloxymethyl)benzotriazole, 1 -(1 -butoxyethyl)benzotriazole
and 1-(1-
cyclohexyloxybutyl) triazole, and combinations thereof.
[00127]
Additional non-limiting examples of the one or more metal deactivators
include 1,2,4-triazoles and derivatives thereof, for example 3 -alkyl(or aryl)-
1,2,4-triazoles,
and Mannich bases of 1,2,4-triazoles, such as 1-[bis(2-ethylhexyl)aminomethyl-
1,2,4-
triazole; alkoxyalky1-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-
triazole; and acylated 3-
amino-1,2,4-triazoles, imidazole derivatives, for example 4,4'-methylenebis(2-
undecy1-5-
methylimidazole) and bis[(N-methypimidazol-2-yllcarbinol octyl ether, and
combinations
thereof.
[00128]
Further non-limiting examples of the one or more metal deactivators
include sulfur-containing heterocyclic compounds, for example 2-
mercaptobenzothiazole,
2,5 -dimercapto- 1 ,3 ,4-thi adiazole and derivatives
thereof; and 3 ,5 -bis [di(2 -
ethylhexypaminomethyl] - 1 ,3 ,4-thiadiazolin-2-one, and combinations thereof.
Even further
non-limiting examples of the one or more metal deactivators include amino
compounds, for
example salicylidenepropylenediamine, salicylaminoguanidine and salts thereof,
and
combinations thereof
Dehazers
[00129]
One or more dehazers can also be included in the= compositions. Non-
limiting examples of dehazers include alkoxylated phenol-formaldehyde
condensates.
Markers
[00130]
One or more markers can also be included in the compositions. The
marker can be used to color the compositions and/or for traceability. Markers
can also allow
for the quantative analysis of additivated fuel at the refinery, on the
roadside, or in the
laboratory. That is, markers can allow for a determination of the amount of
composition
included in the additivated fuel.
Solvents
[00131]
One or more solvents can also be included in the compositions. The
solvents used in the compositions can be inert stable oleophilic (i.e.,
dissolves in fuel) organic
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solvents boiling in the range of about 65 C to 205 C. For example, an
aliphatic or an
aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or
higher-boiling
aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon
atoms, such as
isopropanol, isobutylcarbinol, n-butanol, 2-ethylhexanol, and the like, in
combination with
hydrocarbon solvents, are also suitable for use in the compositions.
The Compositions
[00132] = The compositions are not particularly limited in this
disclosure so long as
it includes the polyalkenylsuccinimide (A), the polyisobutene amine (B), and
the carrier oil
(C).
[00133] In various embodiments, the compositions consist essentially
of, or consist
of, the polyalkenylsuccinimide (A), the polyisobutene amine (B), and the
carrier oil (C). In
embodiments that consist essentially of the polyalkenylsuccinimide (A), the
polyisobutene
amine (B), and the carrier oil (C), the compositions are typically free of
materials or material
compounds that affect the basic properties of the compositions including, but
not limited to,
additional solubilizers.
[00134] In various embodiments, the compositions consist essentially
of, or
consists of, the polyalkenylsuccinimide (A), the polyisobutene amine (B), the
carrier oil (C),
the demulsifier package (D), and solvent. In embodiments that consist
essentially of the
polyalkenylsuccinimide (A), the polyisobutene amine (B), the carrier oil (C),
the demulsifier
package (D), and solvent, the compositions are free of other materials or
material compounds
that affect the basic properties of the compositions.
[00135] In various other embodiments, the compositions are
substantially free of
sulfur. "Substantially free" as used herein in relation to the compositions
being substantially
free of sulfur means that the compositions includes sulfur containing
compounds in an
amount less than about 5, alternatively less than about 4, alternatively less
than about 3,
alternatively less than about 2, alternatively less than about 1,
alternatively less than about
0.5, alternatively less than about 0.25, alternatively 0 parts by weight,
based on 100 parts by
weight of the composition.
[00136] Sulfur limits in fuels in many regions of the globe are less
than 30, less
than 20, or even less than 10 ppm (mg/kg fuel) sulfur. Generally, sulfur
limits in fuels are
moving towards less than 10 ppm sulfur across the globe.' In some embodiments,
the
compositions deliver an amount of sulfur to the fuel which is less than an
amount which can
be detected by instruments and test methods commonly used to detect sulfur
content in fuel.
In various embodiments, the compositions deliver no more sulfur to the fuel
than an amount
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which would "round up" the sulfur content of the unadditivated fuel to the
nearest ppm limit.
In some embodiments, the compositions contribute less than 50, alternatively
less than 25,
alternatively less than 1.5, alternatively less than 1, alternatively less
than 0.5, alternatively
less than 0.2, alternatively less than 0.1, alternatively less than 0.05,
alternatively less than
0.01, mg of sulfur/kg of fuel at the treat rates set forth herein.
[00137] In some embodiments, the compositions include 1 to 75 parts by
weight of
the polyalkenylsuccinimide (A), 15 to 25 parts by weight of the polyisobutene
amine (B), 5 to
70 parts by weight of the carrier oil (C), 2 to 94 parts by weight solvents,
and less than 5 parts
by weight of the demulsifier package (D), based on 100 parts by weight of the
composition.
[00138] In other embodiments, the compositions include 20 to 35 parts
by weight
of the polyalkenylsuccinimide (A), 15 to 25 parts by weight of the
polyisobutene amine (B),
to15 parts by weight of the carrier oil (C), 28 to 55 parts by weight
solvents, less than 5
parts by weight of the demulsifier package (D), and less than 0.5 parts by
weight of the
marker, based on 100 parts by weight of the composition.
[00139] In other embodiments, the compositions include 4 to 15 parts by
weight of
the polyalkenylsuccinimide (A), 30 to 60 parts by weight of the polyisobutene
amine (B), 12-
18 parts by weight of the carrier oil (C), 16 to 20 parts by weight solvents,
0.35 to 0.5 parts
by weight corrosion inhibitors, 0.5 to 3.5 parts by weight dehazers, and 0.5
to 1.5 parts by
weight marker, based on 100 parts by weight of the composition. In one
embodiment, the
compositions include the polyalkenylsuccinimide (A) in an amount of about 6
parts by
weight, the polyisobutene amine (B) in an amount of about 34.67 parts by
weight, and the
carrier oil (C) in an amount of about 15 parts by weight, each based on the
total weight of the
composition.
[00140] The subject disclosure also includes a method of forming the
compositions
comprising the step of mixing the components, e.g. mixing a
polyalkenylsuccinimide (A), a
polyisobutene amine (B), a carrier oil (C), and a demulsifier package (D), and
solvents and
other additives. In various embodiments, the step of mixing is conducted with
no particular
order of addition. For example, all of the components can be mixed in a
single, simultaneous
step to form the compositions. In other embodiments, the step of mixing is
conducted with
an order of addition. For example, in one embodiment, the fatty alcohol
solvent, the
demulsifier package (D), and the marker are mixed together. Then, the aromatic
solvent is
added to the mixture and mixed in, the polyisobutene amine (B) is added to the
mixture and
mixed in, and the carrier oil (C) is added to the mixture and mixed in.
Finally, the
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polyisobutenylsuccinimide (A) is added to the mixture and mixed in to form the
compositions.
[00141] The composition can be used as an additive in fuels, such as
diesel fuel,
gasoline fuel, heating oil, and kerosene or middle distillates. When the
compositions are used
as an additive in diesel fuel, they can be used in any effective amount,
alternatively in an
amount of from 10 to 10,000, alternatively from 10 to 5,000, alternatively
from 50 to 1,000,
mg/kg of diesel fuel. When the compositions are used as an additive in
gasoline fuel, they=
can be used in any effective amount, alternatively in an amount of from 10 to
10,000,
alternatively from 10 to 5,000, alternatively from 50 to 2,000, mg/kg of
gasoline fuel. When
the compositions are used as an additive in heating oil, they can be used in
any effective
amount, alternatively in an amount of from 10 to 1,000, alternatively from 50
to 500, mg/kg
of heating oil.
[00142] The subject disclosure also includes a method of improving the
fuel
economy of an internal combustion engine. The method includes the step of
adding the
compositions to fuel. The compositions can be added to fuel in the amounts set
forth in the
preceding paragraph. For example, in one embodiment of the method, 10 to
10,000 mg of the
compositions is added per kg of fuel.
[00143] The subject disclosure also includes a fuel including the
compositions.
The compositions can be included in the fuel in the amounts set forth above.
For example,
one kg of the fuel can include 10 to 10,000 mg of the composition.
[00144] The following examples are meant to illustrate the disclosure
and are not
to be viewed in any way as limiting to the scope of the disclosure.
EXAMPLES
[00145] A polyisobutenylsuccinimide is formed in accordance with the
instant
disclosure. Specifically, the polyisobutenylsuccinimide is the reaction
product of (1) a
polyisobutene having a chain length of C40 to c200 and an number average
molecular weight
(Mn) of greater than 1,000 g/mol and a content of terminal double bonds of
greater than 75
mol %, (2) maleic anhydride, and (3) tetraethylenepentamine wherein each mol
of
polyisobutene is functionalized with 1 to 2 moles of maleic anhydride.
[00146] The polyisobutenylsuccinimide was added to fuel and the
additivated fuel
was tested to determine fuel economy in accordance with the US Federal Test
Procedure -
Highway Fuel Economy Test (U.S. Environmental Protection Agency Test Protocol,
C.F.R.
Title 40, Part 600, Subpart B) for five different automobiles. Standard U.S.
regular unleaded
gasoline was used in the testing. For each automobile, fuel consumption was
determined first
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with unadditivated fuel and then with additivated fuel formed with a dosage of
190 mg/kg.
The results of the fuel economy testing are set forth in Table 1 below.
TABLE 1
Fuel Economy
Vehicle Model Model Year Engine
Improvement (%)
Dodge Caravan 2008 3.3L V-6 2.50
Mercury Marquis 2007 4.6L V-8 0.69
Chevrolet Uplander 2008 3.9L V-6 1.14
Dodge Journey 2009 3.5L V-6 3.61
Dodge Caravan 2008 3.8L V-6 3.57
Base Fuel: Unadditivated U.S. regular unleaded gasoline
Additive: PIBSI (100 %) based on GLISSOPAL 1000, MSA, and TEPA
Dosage of Additivated Fuel: 190 mg/kg
Crankcase Oil: 10W-30
Test protocol: U.S. Environmental Protection Agency Test Protocol, C.F.R.
Title 40, Part
600, Subpart B
Note: Fuel economy determined by carbon balance.
[00147] Referring now to Table 1, use of the polyisobutenylsuccinimide
in the
additivated fuel resulted in an average fuel savings of 2.3% for the five
automobiles tested.
Further, the fuel economy benefit of the polyisobutenylsuccinimide is even
more astonishing
since it demonstrates almost no activity in any type of High Frequency
Reciprocating Rig
(HFRR) testing and, as is set forth below with Example 1, is miscible with
additional fuel
additives.
[00148] Example 1 is a fuel additive composition which includes the
polyisobutenylsuccinimide and is in accordance with the instant disclosure.
Comparative
Examples 1 and 2 are fuel additive compositions which include fuel economy
additives know
in the art. Specifically, the fuel additive composition of Comparative Example
1 includes a
fatty acid amide and the fuel additive composition of Comparative Example 2
includes a
propoxylated fatty acid amide. The fuel additive compositions of Example 1 and
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Comparative Examples 1 and 2 are set forth in Table 2 below. The amounts set
forth in
Table 2 are parts by weight based on 100 parts by weight of the fuel additive
composition.
[00149]
Further, the fuel additive compositions of Example 1 and Comparative
Examples 1 and 2 were stored at -20 C for 6 weeks and then examined for any
evidence of
phase separation. The phase separation test results are also set forth in
Table 2 below.
TABLE 2
Comparative Comparative
Example 1
Example 1 Example 2
Polyisobutenylsuccinimide
11.1
(according to the subject disclosure)
Fatty Acid Amide
11.1
(according to WO 2009/050256)
Propoxylated Fatty Acid Amide
11.1
(according to WO 2010/005720)
Polyisobutene Amine
10.9 10.9 10.9
(according to the subject disclosure)
Propoxylate Carrier Oil
26.7 26.7 26.7
(according to the subject disclosure)
Paraffinic Solvent 5.8 5.8 5.8
Aromatic Solvent 45.5 45.5 45.5
Total 100.0 100.0
100.0
Phase Separation Test Results One clear
Two phases - Two phases -
(After 6 weeks of storage at -20 C) phase - pass failure
failure
[00150]
Referring now to Table 2, the fuel additive composition of Example 1,
which includes the polyisobutenylsuccinimide, the polyisobutene amine, and the
propoxylate
carrier oil, remains clear and in a single phase even after 6 weeks of storage
at -20 C.
However, the fuel additive compositions of Comparative Examples 1 and 2 form
separate
phases after 6 weeks of storage at -20 C.
[00151]
Example 2 is a fuel additive composition in accordance with the instant
disclosure which includes the= polyisobutenylsuccinimide, the polyisobutene
amine, the
polyether carrier oil, and a demulsifier package. The fuel additive
composition of Example 2
is forth in Table 3 below. To form the fuel additive composition of Example 2,
the fatty
alcohol solvent, the demulsifier components, and the marker are mixed
together. Then, the
aromatic solvent was added to the mixture and mixed in, the polyisobutene
amine was added
to the mixture and mixed in, and the polyether carrier oil was added to the
mixture and mixed
37
=
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in. Finally, the polyisobutenylsuccinimide was added to the mixture and mixed
in to form the
fuel additive composition of Example 2.
TABLE 3
Example 2
% by weight (based Ratio
on 100 parts by Additivated
(Demulsifier
Generic Name weight of the fuel Fuel
Component:
additive (PPM)
PIBSI, by wt.)
composition)
Polyisobutenylsuccinimide 20-35 % 130-303ppm
Polyisobutene Amine 15-25 % 97-217 ppm
Polyether Carrier Oil 5-15 % 32-130 ppm
Marker < 0.5 % < 5 ppm
First Demulsifier < 26 ppm < 1:8
Component
Second Demulsifier
< 1 % < 9 ppm 'í1:14
Component
Third Demulsifier
< 2 % < 17 ppm <0.13
Component
Fatty Alcohol Solvent 8-10 % 52-104 ppm
Aromatic Solvent 20-45 % 130-390 ppm
[00152] Fuel additivated with the fuel additive composition of Example
2 was
tested in accordance with ASTM D 1094 ¨ 07. The test method of ASTM D 1094 ¨
07
determines the miscibility of components in additivated gasoline with water
and the effect of
these components on volume change and on the fuel-water interface. In this
test method, a
sample of fuel was shaken at room temperature with a phosphate buffer solution
in a
graduated cylinder. The cleanliness of the glass cylinder as well as the
change in volume of
the aqueous layer and the appearance of the interface between layers were
taken as the water
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reaction of the fuel. The fuel additivated with the fuel additive composition
of Example 2
was tested and yields a separation rating of (1) (which is the complete
absence of all
emulsions and/or precipitates within either the water layer the treated fuel
layer), and has
minimal lacing at the interface between the fuel and water layers. As such,
the fuel additive
composition of Example 2, which includes a polyisobutenylsuccinimide, a
polyisobutene
amine, a polyether carrier oil, and a demulsifier package, was resistant to
emulsification upon
exposure to water.
[00153] Referring now to Table 4, the miscibility of the fuel
additivated with the
fuel additive composition of Example 2 with water was also tested over a
repetitive timing
cycle in a multi-contact test. In this test, each individual cycle is referred
to as a contact.
Specifically, 200 ml of fuel additivated with the fuel additive composition of
Example 2 was
mixed with 20 ml of water in a glass container and shaken for 5 minutes at the
highest setting
on a mechanical reciprocating shaker. The sample is then held, with no
agitation, for 24
hours and observations regarding the fuel layer, the water layer, and any
interface
therebetween are made. The fuel is then decanted from the glass container, and
200 ml of
fresh fuel additivated with the fuel additive composition of Example 2 are
added to the glass
container and the cycle was repeated 10 times, with the results set forth in
Table 4. The
contact number is the number of times the additivated fuel and the water have
come into
contact, thus there are 10 contacts per test, with each contact 24 hours
apart.
[00154] Emulsion observations regarding the mixture of the fuel
additive
composition of Example 2 and water were made as follows:
0) Both the water layer and the fuel layer are clean with no lacing skin, or
bubbles;
1) Slight skin at the interface between the water and the fuel layer that does
not break
on tilting the bottle;
2) Slight skin at the oil-water interface, heavier than 1) and usually
accompanied by
dirt and bubbles on the skin (no evidence of emulsion);
3) Minimal amounts of emulsion at the bottom and in the center of the bottle.
It is
=
circular in shape and approximately 1/4 to 1 inch in diameter;
4) Emulsion at the interface between the water and the fuel layer
(approximately the
same amount of emulsion on the bottom of the bottle as 3);
5) Emulsion at bottom on the bottle expands upward and the thickness of the
emulsion at the interface slightly thicker than 4).
6) Emulsion amounts increase with an emulsion film forming on sides of bottle
surrounding the water layer;
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7) Emulsion on bottom of water layer is almost solid and the water layer is
barely
visible;
8) Emulsion with bubbles and the water layer is non longer visible;
9) Emulsion with fewer greater than 75 % of the emulsion is solid;
10) Emulsion is almost completely solid, with only a few air bubbles visible;
and
11) Emulsion is completely solid.
[00155] Further, observations regarding the water layer and the fuel
layer were
made with "C" for clear and "H" for hazy.
TABLE 4
Contact
The Water Layer The Fuel Layer Interface
Number
1C C 0
2 C C 0
3 C C 0
4 C C 1
C C 2
6 C C 2
7 C C 2
8 C C1
9 C C1
C C 2
7 Days Later C C 2
[00156] Referring now to Table 4, the fuel additive composition of
Example 2,
which includes the polyisobutenylsuccinimide, the polyisobutene amine, the
polyether carrier
oil, and the demulsifier package, was resistant to emulsification upon
exposure to multi-
contact exposure to water.
[00157] Referring now to Table 5, the storage stability of the fuel
additive
composition of Example 2 was also tested at 23 C and -15 C. To test storage
stability, 100
ml the fuel additive composition of Example 2 was added to a centrifuge
container which has
a conical bottom end. The centrifuge container is typically clear, and has
amount marks on
the side thereof The conical portion of the centrifuge container is about the
size of a
sharpened pencil tip. The samples were held for 4 weeks, with weekly
observations made
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regarding the amount of phase separation and sediment formed. After testing a
digital photo
of the conical tip of the centrifuge container was taken.
TABLE 5
Week 23 C -15 C
Phase
Phase Separation
SedimentSediment
Separation
1 None None None None
2 None None None None
3 None None None None
4 None None None None
[00158] Referring now to Table 5, the fuel additive composition of
Example 2,
which includes a polyisobutenylsuccinimide, a polyisobutene amine, a polyether
carrier oil,
and a demulsifier package, remained clear and in a single phase even after 4
weeks of storage
at 23 C and -15 C. Further, little (less than .05 ml per 100 ml of
composition) or no
sediment forms on the bottom of the clear centrifuge container.
[00159] It is to be understood that the appended claims are not limited
to express
and particular compounds, compositions, or methods described in the detailed
description,
which may vary between particular embodiments which fall within the scope of
the appended
claims. With respect to any Markush groups relied upon herein for describing
particular
features or aspects of various embodiments, it is to be appreciated that
different, special,
and/or unexpected results may be obtained from each member of the respective
Markush
group independent from all other Markush members. Each member of a Markush
group may
be relied upon individually and or in combination and provides adequate
support for specific
embodiments within the scope of the appended claims.
[00160] It is also to be understood that any ranges and subranges
relied upon in
describing various embodiments of the present disclosure independently and
collectively fall
within the scope of the appended claims, and are understood to describe and
contemplate all
ranges including whole and/or fractional values therein, even if such values
are not expressly
written herein. One of skill in the art readily recognizes that the enumerated
ranges and
subranges sufficiently describe and enable various embodiments of the present
disclosure,
and such ranges and subranges may be further delineated into relevant halves,
thirds,
quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9"
may be further
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delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e.,
from 0.4 to 0.6, and an
upper third, i.e., from 0.7 to 0.9, which individually and collectively are
within the scope of
the appended claims, and may be relied upon individually and/or collectively
and provide
adequate support for specific embodiments within the scope of the appended
claims. In
addition, with respect to the language which defines or modifies a range, such
as "at least,"
"greater than," "less than," "no greater than," and the like, it is to be
understood that such
language includes subranges and/or an upper or lower limit. As another
example, a range of
"at least 10" inherently includes a subrange of from at least 10 to 35, a
subrange of from at
least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may
be relied upon
individually and/or collectively and provides adequate support for specific
embodiments
within the scope of the appended claims. Finally, an individual number within
a disclosed
range may be relied upon and provides adequate support for specific
embodiments within the
scope of the appended claims. For example, a range "of from 1 to 9" includes
various
individual integers, such as 3, as well as individual numbers including a
decimal point (or
fraction), such as 4.1, which may be relied upon and provide adequate support
for specific
embodiments within the scope of the appended claims.
[00161] In addition, it is contemplated that the weight percents or
other numerical
values or ranges of values described above may vary and may be further defined
as any value
or range of values, both whole and fractional, within those ranges and values
described above
and/or may vary from the values and/or range of values above by 5%, 10%,
15%,
20%, 25%, 30%, etc, so long as the variations remain within the scope of
the disclosure.
As one example, any of the numerical values or ranges described herein may be
further
defined as "about" and, as such, may vary in accordance with this paragraph.
As used in the
preceding sentence the word about means reasonably close to.
[00162] The disclosure has been described in an illustrative manner,
and it is to be
understood that the terminology which has been used is intended to be in the
nature of words
of description rather than of limitation. Many modifications and variations of
the present
disclosure are possible in light of the above teachings, and the disclosure
may be practiced
otherwise than as specifically described.
42
