TECHNICAL FIELD
[0001] This disclosure is directed to fuel additives for spark-ignition engines providing
enhanced engine, intake valve, and/or injector performance, to fuel compositions including
such additives, and to methods for using such fuel additives in a fuel composition
for improved performance.
BACKGROUND
[0002] Fuel compositions for vehicles are continually being improved to enhance various
properties of the fuels in order to accommodate their use in newer, more advanced
engines including both gasoline port fuel injected engines as well as gasoline direct
injected engines. Often, improvements in fuel compositions center around improved
fuel additives and other components used in the fuel. For example, friction modifiers
may be added to fuel to reduce friction and wear in the fuel delivery systems of an
engine. Other additives may be included to reduce the corrosion potential of the fuel
or to improve the conductivity properties. Still other additives may be blended with
the fuel to improve fuel economy. Engine and fuel delivery system deposits represent
another concern with modern combustion engines, and therefore other fuel additives
often include various deposit control additives to control and/or mitigate engine
deposit problems. Thus, fuel compositions typically include a complex mixture of additives.
[0003] However, there remain challenges when attempting to balance such a complex assortment
of additives. For example, some of the conventional fuel additives may be beneficial
for one characteristic or one type of engine, but at the same time be detrimental
to another characteristic of the fuel. In some instances, fuel additives effective
in gasoline port fuel injection engines (PFI) do not necessarily provide comparable
performance in gasoline direct injection engines (GDI) and vice versa. In yet other
circumstances, fuel additives often require an unreasonably high treat rate to achieve
desired effects, which tends to place undesirable limits on the available amounts
of other additives in the fuel composition. Yet other fuel additives tend to be expensive
and/or difficult to manufacture or incorporate in fuels.
SUMMARY
[0004] In one embodiment or approach, a fuel additive or fuel additive package for a spark-ignition
engine is described herein to provide improved engine performance and includes a Mannich
detergent including the reaction product of a hydrocarbyl-substituted phenol or cresol,
one or more aldehydes, and one or more amines; a succinimide detergent prepared by
reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine,
or alkyl amine having one or more primary, secondary, or tertiary amino groups; and
wherein a weight ratio of the Mannich detergent to the succinimide detergent is from
about 15:1 to about 30:1. As discussed more herein, such weight ratios provide a synergistic
effect with improved engine and/or injector performance in both port fuel injection
(PFI) engines as well as gasoline direct injection (GDI) engines.
[0005] In other embodiments or approaches, the fuel additive of the previous paragraph may
include one or more optional features or embodiments in any combination. The optional
features or embodiments may include one or more of the following: wherein the weight
ratio of the Mannich detergent to the succinimide detergent is from about 20:1 to
about 30:1; and/or wherein the Mannich detergent has the structure of Formula I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0001)
wherein R
1 of Formula I is hydrogen or a C1 to C4 alkyl group, R
2 of Formula I is a hydrocarbyl group having a number average molecular weight of about
500 to about 3000, R
3 of Formula I is a C1 to C4 alkylene or alkenyl group (preferably a C1 group), and
R
4 and R
5 of Formula I are, independently, hydrogen, a linear or branched C1 to C12 alkyl group,
or a mono or di(C1 to C4)alkyl amino C1-C12 alkyl group; and/or wherein R
2 of Formula I is polyisobutenyl having a number average molecular weight of about
500 to about 1500; and/or wherein the succinimide detergent is a hydrocarbyl substituted
mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or
a combination thereof; and/or wherein the hydrocarbyl-substituted succinic acylating
agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl group
has a number average molecular weight of about 450 to about 3000, and wherein a molar
ratio of the hydrocarbyl-substituted succinic anhydride to the amine, polyamine, or
alkyl amine is from about 0.5: 1 to about 2:1; and/or wherein the hydrocarboyl-substituted
succinic anhydride is polyisobutylene substituted succinic anhydride, and wherein
the polyisobutylene has a number average molecular weight of about 500 to about 1200
as measured by GPC using polystyrene as reference; and/or wherein the amine, polyamine,
or alkyl amine is tetraethylene pentamine (TEPA), triethylene tetraamine (TETA), or
a polyamine or alkyl amine having the formula H
2N-((CHR
20-(CH
2)
q-NH)
r-H, wherein R
20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q is an integer
of from 1 to 4 and r is an integer of from 1 to 6, and mixtures thereof; and/or wherein
the amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA); and/or further
comprising an alkoxylated alcohol, and wherein a weight ratio of the alkoxylated alcohol
to the Mannich detergent is about 1.0 or less (preferably 0.8 or less, 0.6 or less,
or 0.5 or less); and/or wherein the alkoxylated alcohol is a polyether prepared by
reacting an alkyl alcohol or an alkylphenol with an alkylene oxide selected from ethylene
oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof;
and/or wherein the alkoxylated alcohol is a polyether having the structure of Formula
III:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0002)
wherein R
6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group
having 5 to 50 carbons, R
7 of Formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and/or
wherein the fuel additive includes about 20 to about 60 weight percent of the Mannich
detergent, about 0.5 to about 10 weight percent of the succinimide detergent, and
about 5 to about 30 weight percent of an alkoxylated alcohol. Values of number average
molecular weight as disclosed herein are measured by GPC using polystyrene as reference.
[0006] In another approach or embodiment, a gasoline fuel composition providing improved
engine and/or injector performance in both port fuel injection (PFI) engines as well
as gasoline direct injection (GDI) engines is described herein. The gasoline fuel
composition includes about 15 to about 300 ppmw of a Mannich detergent including the
reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes,
and one or more amines; about 0.5 to about 20 ppmw of a succinimide detergent prepared
by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine,
or alkyl amine having one or more primary, secondary, or tertiary amino groups; wherein
a weight ratio of the Mannich detergent to the succinimide detergent is from about
15:1 to about 30: 1; and about 5 to about 150 ppmw of an alkoxylated alcohol. In further
embodiments, the gasoline fuel composition may also include any of the optional features
or embodiments as described above with respect to the fuel additive.
[0007] In yet other approaches or embodiments, a method of reducing deposits in a gasoline
engine is described herein. The method includes operating a gasoline engine on a fuel
composition containing a major amount of a gasoline fuel and a minor amount of a fuel
additive by injecting the gasoline fuel through one or more injectors; wherein the
fuel additive includes (i) a Mannich detergent including the reaction product of a
hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines;
(ii) a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic
acylating agent with an amine, polyamine, or alkyl amine having one or more primary,
secondary, or tertiary amino groups; and (iii) wherein the fuel additive has a weight
ratio of the Mannich detergent to the succinimide detergent of about 15:1 to about
30:1; and wherein the fuel additive reduces deposits in the gasoline engine.
[0008] In other embodiments or approaches, the method described in the previous paragraph
may be include one or more optional features, method steps, or embodiments in any
combination. The optional features, steps, or embodiments may include one or more
of the following: wherein the fuel additive reduces deposits in a port fuel injection
(PFI) engine, a gasoline direct injection (GDI) engine, or both; and/or wherein the
reduced deposits are reduced injector deposits measured by one of injector pulse width,
injection duration, injector flow, or combinations thereof; and/or wherein the fuel
additive reduces deposits when sprayed from an injector configured to spray droplets
of about 10 to about 30 microns, about 120 to about 200 microns, or both; and/or wherein
the weight ratio of the Mannich detergent to the succinimide detergent is from about
20:1 to about 30:1; and/or wherein the Mannich detergent has the structure of Formula
I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0003)
wherein one of R
1 and R
2 of Formula I is hydrogen or a C1 to C4 alkyl group, the other of R
1 and R
2 is a hydrocarbyl group having a number average molecular weight of about 500 to about
3000, R
3 of Formula I is a C1 to C4 alkylene or alkenyl group, and R
4 and R
5 of Formula I are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or
di(C1 to C4)alkyl amino C1-C12 alkyl group; and/or wherein R
2 of Formula I is polyisobutenyl having a number average molecular weight of about
500 to about 1500; and/or wherein the succinimide detergent is a hydrocarbyl substituted
mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or
a combination thereof; and/or wherein the hydrocarbyl-substituted succinic acylating
agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl group
has a molecular weight of about 450 to about 3000, and wherein a molar ratio of the
hydrocarbyl-substituted succinic anhydride to the amine, polyamine, or alkyl amine
is from about 0.5:1 to about 2:1; and/or wherein the hydrocarboyl-substituted succinic
anhydride is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene
has a number average molecular weight of about 500 to about 1200 as measured by GPC
using polystyrene as reference; and/or wherein the amine, polyamine, or alkyl amine
is tetraethylene pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine or
alkyl amine having the formula H
2N-((CHR
20-(CH
2)
q-NH)
r-H, wherein R
20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q is an integer
of from 1 to 4 and r is an integer of from 1 to 6, and mixtures thereof; and/or wherein
the amine, polyamine, or alkyl amine is tetraethylene pentamine (TEPA); and/or further
comprising an alkoxylated alcohol and wherein a weight ratio of the alkoxylated alcohol
to the Mannich detergent is about 1.0 or less; and/or wherein the alkoxylated alcohol
is a polyether prepared by reacting an alkyl alcohol or an alkylphenol with an alkylene
oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof,
or combinations thereof; and/or wherein the alkoxylated alcohol is a polyether having
the structure of Formula III:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0004)
wherein R
6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group
having 5 to 50 carbons, R
7 of Formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and/or
wherein the fuel additive includes about 20 to about 60 weight percent of the Mannich
detergent, about 0.5 to about 10 weight percent of the succinimide detergent, and
about 5 to about 30 weight percent of the alkoxylated alcohol. Values of number average
molecular weight as disclosed herein are measured by GPC using polystyrene as reference.
[0009] In yet other approaches or embodiments, the use of a fuel additive package as described
by any embodiment herein or the use of a gasoline fuel as described by any embodiment
of the fuel composition herein for improving the injector performance of a port fuel
injection (PFI) engine, a gasoline direct injection (GDI) engine, or both the PFI
and GDI engine.
[0010] In any embodiment of the fuel additive package, the fuel, the method, or the use
herein, the fuel additive package of this disclosure may be free of quaternary ammonium
salt detergents, and preferably, free of quaternary ammonium internal salt detergents
that are obtained from amines or polyamines and substantially devoid of any free anion
species. In this context, free of means less than 0.5 ppmw, less than 0.1 ppmw, less
than 0.05 ppmw or, preferably, none.
BRIEF DESCRIPTION OF DRAWING FIGURES
[0011]
FIG. 1 is a graph showing GDI dirty-up (DU) and clean-up (CU) of Comparative and Inventive
fuel additives; and
FIG. 2 is a graph showing GDI dirty-up (DU) and clean-up (CU) of Comparative and Inventive
fuel additives.
DETAILED DESCRIPTION
[0012] The present disclosure provides fuel additives including combinations of Mannich
detergent(s) and succinimide detergent(s) discovered effective in certain weight ratios
to provide improved engine and/or injector performance in both port fuel injection
(PFI) engines as well as gasoline direct injection (GDI) engines. The fuel additives,
in some approaches, may also include alkoxylated alcohols and, when included, certain
ratios of the alkoxylated alcohol to the Mannich detergent. Also provided herein are
fuel compositions including the novel fuel additive combinations and methods of using
or combusting a fuel including the fuel additive combinations herein to achieve improved
engine, intake valve, and/or injector performance. As noted more below, the fuel additives
herein include a synergistic combination of Mannich detergent(s) and succinimide detergent(s)
when used in a weight ratio of the Mannich detergent to the succinimide detergent
of about 15:1 to about 30:1. Mannich detergents alone do not provide any clean-up
performance in GDI engines, but surprisingly achieve improved clean-up when combined
in certain ratios with succinimide detergents.
[0013] In aspects or embodiments of this disclosure, improved engine, intake valve, and/or
injector performance of the fuel additive combinations herein may include one or more
of controlling or reducing fuel injector deposits, controlling or reducing intake
valve deposits, controlling or reducing combustion chamber deposits and/or controlling
or reducing intake valve sticking in PFI engines, GDI engines, or both types of engines.
Improved injector performance may also be one or more of improved fuel flow, improved
fuel economy, and/or improved engine efficiency as determined via one or more of injector
pulse width, injection duration, and/or injector flow.
Mannich Detergent
[0014] In one aspect, the fuel additives and fuels herein first include one or more Mannich
detergent(s). Suitable Mannich detergents include the reaction product(s) of an alkyl-substituted
hydroxyaromatic or phenol compound, aldehyde, and amine as discussed more below.
[0015] In one approach, the alkyl substituents of the hydroxyaromatic compound may include
long chain hydrocarbyl groups on a benzene ring of the hydroxyaromatic compound and
may be derived from an olefin or polyolefin having a number average molecular weight
(Mn) from about 500 to about 3000, preferably from about 700 to about 2100, as determined
by gel permeation chromatography (GPC) using polystyrene as reference. The polyolefin,
in some approaches, may also have a polydispersity (weight average molecular weight/number
average molecular weight) of about 1 to about 10 (in other instances, about 1 to about
4 or about 1 to about 2) as determined by GPC using polystyrene as reference.
[0016] The alkylation of the hydroxyaromatic or phenol compound is typically performed in
the presence of an alkylating catalyst at a temperature in the range of about 0 to
about 200°C, preferably 0 to about 100°C. Acidic catalysts are generally used to promote
Friedel-Crafts alkylation. Typical catalysts used in commercial production include
sulphuric acid, BF
3, aluminum phenoxide, methanesulphonic acid, cationic exchange resin, acidic clays
and modified zeolites.
[0017] Polyolefins suitable for forming the alkyl-substituted hydroxyaromatic compounds
of the Mannich detergents include polypropylene, polybutenes, polyisobutylene, copolymers
of butylene and/or butylene and propylene, copolymers of butylene and/or isobutylene
and/or propylene, and one or more mono-olefinic comonomers copolymerizable therewith
(e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.) where a copolymer
molecule contains at least 50% by weight, of butylene and/or isobutylene and/or propylene
units. Any comonomers polymerized with propylene or butenes may be aliphatic and can
also contain non-aliphatic groups, e.g., styrene, o-methylstyrene, p-methylstyrene,
divinyl benzene and the like if needed. Thus, the resulting polymers and copolymers
used in forming the alkyl-substituted hydroxyaromatic compounds are substantially
aliphatic hydrocarbon polymers.
[0018] Polybutylene is preferred for forming the hydrocarbyl-substituted hydroxyaromatic
or phenol compounds herein. Unless otherwise specified herein, the term "polybutylene"
is used in a generic sense to include polymers made from "pure" or "substantially
pure" 1-butene or isobutene, and polymers made from mixtures of two or all three of
1-butene, 2-butene and isobutene. Commercial grades of such polymers may also contain
insignificant amounts of other olefins. So-called high reactivity polyisobutenes having
relatively high proportions of polymer molecules having a terminal vinylidene group
are also suitable for use in forming the long chain alkylated phenol reactant. Suitable
high-reactivity polyisobutenes include those polyisobutenes that comprise at least
about 20% of the more reactive methylvinylidene isomer, preferably at least 50% and
more preferably at least 70%. Suitable polyisobutenes include those prepared using
BF
3 catalysts. The preparation of such polyisobutenes in which the methylvinylidene isomer
comprises a high percentage of the total composition is described in
US 4,152,499 and
US 4,605,808, which are both incorporated herein by reference.
[0019] The Mannich detergent, in some approaches or embodiments, may be made from an alkylphenol
or alkylcresol. However, other phenolic compounds may be used including alkyl-substituted
derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol,
phenethylphenol, naphthol, tolylnaphthol, among others. Preferred for the preparation
of the Mannich detergents are the polyalkylphenol and polyalkylcresol reactants, e.g.,
polypropyl phenol, polybutylphenol, polypropylcresol and polybutylcresol, wherein
the alkyl group has a number average molecular weight of about 500 to about 3000 or
about 500 to about 2100 as measured by GPC using polystyrene as reference, while the
most preferred alkyl group is a polybutyl group derived from polyisobutylene having
a number average molecular weight in the range of about 700 to about 1300 as measured
by GPC using polystyrene as reference.
[0020] The preferred configuration of the alkyl-substituted hydroxyaromatic compound is
that of a para-substituted mono-alkylphenol or a para-substituted mono-alkyl ortho-cresol.
However, any hydroxyaromatic compound readily reactive in the Mannich condensation
reaction may be employed. Thus, Mannich products made from hydroxyaromatic compounds
having only one ring alkyl substituent, or two or more ring alkyl substituents are
suitable for forming this detergent additive. The alkyl substituents may contain some
residual unsaturation, but in general, are substantially saturated alkyl groups.
[0021] In approaches or embodiments, representative amine reactants suitable to form the
Mannich detergent herein include, but are not limited to, alkylene polyamines having
at least one suitably reactive primary or secondary amino group in the molecule. Other
substituents such as hydroxyl, cyano, amido, etc., can be present in the polyamine.
In a one embodiment, the alkylene polyamine is a polyethylene polyamine. Suitable
alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylene pentamine and mixtures of such amines having nitrogen contents corresponding
to alkylene polyamines of the formula H
2N--(A-NH--)
nH, where A in this formula is divalent ethylene or propylene and n is an integer of
from 1 to 10, preferably 1 to 4. The alkylene polyamines may be obtained by the reaction
of ammonia and dihalo alkanes, such as dichloro alkanes.
[0022] The amine may also be an aliphatic diamine having one primary or secondary amino
group and at least one tertiary amino group in the molecule. Examples of suitable
polyamines include N,N,N",N"-tetraalkyldialkylenetriamines (two terminal tertiary
amino groups and one central secondary amino group), N,N,N',N"-tetraalkyltrialkylene
tetramines (one terminal tertiary amino group, two internal tertiary amino groups
and one terminal primary amino group), N,N,N',N",N‴-pentaalkyltrialkylenetetramines
(one terminal tertiary amino group, two internal tertiary amino groups and one terminal
secondary amino group), N,N'-dialkylamine, N,N-dihydroxyalkyl-alpha-, omega-alkylenediamines
(one terminal tertiary amino group and one terminal primary amino group), N,N,N'-trihydroxyalkyl-alpha,
omega-alkylenediamines (one terminal tertiary amino group and one terminal secondary
amino group), tris(dialkylaminoalkyl) aminoalkylmethanes (three terminal tertiary
amino groups and one terminal primary amino group), and similar compounds, wherein
the alkyl groups are the same or different and typically contain no more than about
12 carbon atoms each, and which preferably contain from 1 to 4 carbon atoms each.
Most preferably these alkyl groups are methyl and/or ethyl groups. Preferred polyamine
reactants are N,N-dialkyl-alpha, omega-alkylene diamine, such as those having from
3 to about 6 carbon atoms in the alkylene group and from 1 to about 12 carbon atoms
in each of the alkyl groups, which most preferably are the same but which can be different.
Exemplary amines may include N,N-dimethyl-1,3-propanediamine and/or N-methyl piperazine.
[0023] Examples of polyamines having one reactive primary or secondary amino group that
can participate in the Mannich condensation reaction, and at least one sterically
hindered amino group that cannot participate directly in the Mannich condensation
reaction to any appreciable extent include N-(tert-butyl)-1,3-propanediamine, N-neopentyl-1,3-propane
diamine-, N-(
tert-butyl)-1-methyl-1,2-ethanediamine, N-(tert-butyl)-1-methyl-1,3-propane diamine, and
3,5-di(tert-butyl)aminoethylpiperazine.
[0024] In approaches or embodiments, representative aldehydes for use in the preparation
of the Mannich detergents herein include the aliphatic aldehydes such as formaldehyde,
acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde,
stearaldehyde. Aromatic aldehydes which may be used include benzaldehyde and salicylaldehyde.
Illustrative heterocyclic aldehydes for use herein are furfural and thiophene aldehyde,
etc. Also useful are formaldehyde-producing reagents such as paraformaldehyde, or
aqueous formaldehyde solutions such as formalin. Most preferred is formaldehyde or
formalin.
[0025] The condensation reaction among the alkylphenol, the specified amine(s) and the aldehyde
may be conducted at a temperature typically in the range of about 40°C to about 200°C.
The reaction can be conducted in bulk (no diluent or solvent) or in a solvent or diluent.
Water is evolved and can be removed by azeotropic distillation during the course of
the reaction. Typically, the Mannich reaction products are formed by reacting the
alkyl-substituted hydroxyaromatic compound, the amine and aldehyde in the molar ratio
of 1.0:0.5-2.0:1.0-3.0, respectively. Suitable Mannich base detergents include those
detergents taught in
US 4,231,759;
US 5,514,190;
US 5,634,951;
US 5,697,988;
US 5,725,612; and
5,876,468, the disclosures of which are incorporated herein by reference.
[0026] In other approaches or embodiments, suitable Mannich detergents for the fuel additives
herein may have a structure of Formula I below:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0005)
wherein one of R
1 and R
2 of Formula I is hydrogen or a C1 to C4 alkyl group, the other of R
1 and R
2 is a hydrocarbyl group having a number average molecular weight of about 500 to about
3000, R
3 of Formula I is a C1 to C4 alkylene or alkenyl linking group, and R
4 and R
5 of Formula I are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or
di(C1 to C4)alkyl amino C1-C12 alkyl group. In one aspect, R
1 of Formula I is hydrogen or a C1 to C4 alkyl group, R
2 of Formula I is a hydrocarbyl group having a number average molecular weight of about
500 to about 3000 (or about 500 to about 2100, or about 500 to about 1800, or about
500 to about 1500). In another aspect, R
1 of Formula I is hydrogen or a C1 to C4 alkyl group, and R
2 of Formula I is a polyisobutenyl group having a number average molecular weight of
about 500 to about 1500. Values of number average molecular weight as disclosed herein
are measured by GPC using polystyrene as reference.
[0027] A fuel additive or additive package may include about 20 to about 60 weight percent
of the above-described Mannich detergent, about 25 to about 50 weight percent of the
Mannich detergent, or about 30 to about 45 weight percent of the Mannich detergent
(based on the total weight of the active Mannich detergent in the fuel additive).
When blended into a gasoline fuel, the fuel composition may include about 15 ppmw
to about 300 ppmw of the above-described Mannich detergent, about 25 ppmw to about
155 ppmw, or about 55 ppmw to about 125 ppmw of the Mannich detergent in the fuel
composition (active Mannich detergent treat rates). In some embodiments, the fuel
additives herein includes a single type of Mannich detergents.
Succinimide Detergents
[0028] The fuel additives or fuels herein may also include one or more hydrocarbyl-substituted
dicarboxylic anhydride derivatives, and preferably, one or more hydrocarbyl-substituted
succinimide detergents. In one approach, this additive may be prepared by reacting
a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkyl
amine having one or more primary, secondary, or tertiary amino groups. In some embodiments,
the hydrocarbyl substituted dicarboxylic anhydride derivative includes hydrocarbyl
succinimides, succinamides, succinimide-amides and succinimide-esters. These nitrogen-containing
derivatives of hydrocarbyl succinic acylating agents may be prepared by reacting a
hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkyl
amine having one or more primary, secondary, or tertiary amino groups. The succinimide
detergents may be mono-succinimides, bis-succinimides, or combinations thereof.
[0029] In some approaches or embodiments, the hydrocarbyl substituted dicarboxylic anhydride
derivative may include a hydrocarbyl substituent having a molecular weight or a number
average molecular weight ranging from about 450 to about 3000 as measured by GPC using
polystyrene as reference. The derivative may be selected from a diamide, acid/amide,
acid/ester, diacid, amide/ester, diester, and imide. Such derivative may be made from
reacting a hydrocarbyl substituted dicarboxylic anhydride with ammonia, a polyamine,
or an alkyl amine having one or more primary, secondary, or tertiary amino groups.
In some embodiments, the polyamine or alkyl amine may be tetraethylene pentamine (TEPA),
triethylenetetramine (TETA), and the like amines. In other approaches, the polyamine
or alkyl amine may have the formula H
2N-((CHR
20-(CH
2)
q-NH)
r-H, wherein R
20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q is an integer
of from 1 to 4 and r is an integer of from 1 to 6, and mixtures thereof. In other
approaches, a molar ratio of the hydrocarbyl substituted dicarboxylic anhydride reacted
with the ammonia, polyamine, or alkyl amine may be from about 0.5:1 to about 2:1,
in other approaches about 1:1 to about 2:1, or in other approaches, about 1:1 to about
1.6:1.
[0030] In other approaches, the hydrocarbyl substituted dicarboxylic anhydride may be a
hydrocarbyl carbonyl compound of the Formula IV:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0006)
where R
10 of Formula IV is a hydrocarbyl group derived from a polyolefin. In some aspects,
the hydrocarbyl carbonyl compound may be a polyalkylene succinic anhydride reactant
wherein R
10 is a hydrocarbyl moiety, such as for example, a polyalkenyl radical having a number
average molecular weight of from about 450 to about 3000 as measured by GPC using
polystyrene as reference. For example, the number average molecular weight of R
10 may range from about 600 to about 2500, or from about 700 to about 1500 or about
850 to about 1000, as measured by GPC using polystyrene as reference. A particularly
useful R
10 of Formula IV has a number average molecular weight of about 900 to about 1000 Daltons
(as measured by GPC using polystyrene as reference) and comprises polyisobutylene.
Unless indicated otherwise, molecular weights in the present specification are number
average molecular weights as measured by GPC using polystyrene as reference.
[0031] The R
10 hydrocarbyl moiety of Formula IV may include one or more polymer units chosen from
linear or branched alkenyl units. In some aspects, the alkenyl units may have from
about 2 to about 10 carbon atoms. For example, the polyalkenyl radical may comprise
one or more linear or branched polymer units chosen from ethylene radicals, propylene
radicals, butylene radicals, pentene radicals, hexene radicals, octene radicals and
decene radicals. In some aspects, the R
10 polyalkenyl radical may be in the form of, for example, a homopolymer, copolymer
or terpolymer. In one aspect, the polyalkenyl radical is isobutylene. For example,
the polyalkenyl radical may be a homopolymer of polyisobutylene comprising from about
10 to about 60 isobutylene groups, such as from about 20 to about 30 isobutylene groups.
The polyalkenyl compounds used to form the R
10 polyalkenyl radicals may be formed by any suitable methods, such as by conventional
catalytic oligomerization of alkenes.
[0032] In some aspects, high reactivity polyisobutenes having relatively high proportions
of polymer molecules with a terminal vinylidene group may be used to form the R
10 group. In one example, at least about 60%, such as about 70% to about 90%, of the
polyisobutenes comprise terminal olefinic double bonds. High reactivity polyisobutenes
are disclosed, for example, in
US 4,152,499, the disclosure of which is herein incorporated by reference in its entirety.
[0033] In some aspects, approximately one mole of maleic anhydride may be reacted per mole
of polyalkylene, such that the resulting polyalkenyl succinic anhydride has about
0.8 to about 1 succinic anhydride group per polyalkylene substituent. In other aspects,
the molar ratio of succinic anhydride groups to polyalkylene groups may range from
about 0.5 to about 3.5, such as from about 1 to about 1.1.
[0034] The hydrocarbyl carbonyl compounds may be made using any suitable method. One example
of a method for forming a hydrocarbyl carbonyl compound comprises blending a polyolefin
and maleic anhydride. The polyolefin and maleic anhydride reactants are heated to
temperatures of, for example, about 150°C to about 250°C, optionally, with the use
of a catalyst, such as chlorine or peroxide. Another exemplary method of making the
polyalkylene succinic anhydrides is described in
US 4,234,435, which is incorporated herein by reference in its entirety.
[0035] In the hydrocarbyl substituted dicarboxylic anhydride derivative, the polyamine reactant
may be an alkylene polyamine. For example, the polyamine may be selected from ethylene
polyamine, propylene polyamine, butylenes polyamines, and the like. In one approach,
the polyamine is an ethylene polyamine that may be selected from ethylene diamine,
diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene
hexamine, and N, N'-(iminodi-2,1,ethanediyl) bis-1,3- propanediamine. A particularly
useful ethylene polyamine is a compound of the formula H
2N-((CHR
1-(CH
2)
q-NH)
r-H, wherein R
1 thereof is hydrogen, q is 1 and r is 4.
[0036] In yet further approaches, the hydrocarbyl substituted dicarboxylic anhydride derivative
is a compound of Formula V
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0007)
wherein R
10 of Formula V is a hydrocarbyl group (such as polyisobutylene and/or the other above
described R
10 moieties) and R
11 of Formula V is a hydrogen, an alkyl group, an aryl group, -OH, -NHR
12, or a polyamine, or an alkyl group containing one or more primary, secondary, or
tertiary amino groups. In some approaches, R
11 of Formula V is derived from ethylene diamine, diethyelene triamine, triethylene
tetraamine, tetraethylene pentamine, pentaethylene hexamine, N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine
and combinations thereof. In some embodiments, R
10 of Formula V is a hydrocarbyl group and R
11 is hydrogen, an alkyl group, an aryl group, -OH, -NHR
12, or a polyamine and wherein R
12 thereof is a hydrogen or an alkyl group. In other embodiments, the additive of Formula
V includes a hydrocarbyl substituted succinimide derived from ethylene diamine, diethylene
triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine,
N,N'-(iminodi-2,1,ethanediyl)bis-1,3-propanediamine and combinations thereof. In still
other embodiments, R
10 in the compound of Formula V is a hydrocarbyl group having a number average molecular
weight from about 450 to about 3,000 and R
11 is derived from tetraethylene pentamine and derivatives thereof.
[0037] In yet other approaches, R
11 is a radical of Formula VI
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0008)
wherein A is NR
12 or an oxygen atom, R
12, R
13, and R
14 of Formula VI are independently a hydrogen atom or an alkyl group, m and p are integers
from 2 to 8; and n is an integer from 0 to 4. In some approaches, R
13 and R
14 of Formula VI, together with the nitrogen atom to which they are attached, form a
5 membered ring.
[0038] In approaches or embodiments, the succinimide detergent herein is a hydrocarbyl substituted
mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide detergent, or
a combination thereof. In one approach or embodiment, the succinimide detergent may
be derived from polyisobutylene succinic anhydride and the amine in a 1:1 to a 1:6
molar ratio.
[0039] A fuel additive or the fuel herein may include about 0.5 to about 10 weight percent
of the active succinimide detergent, about 0.5 to about 8 weight percent of the succinimide
detergent, or about 1 to about 5 weight percent of the succinimide detergent (based
on the total weight of the active succinimide within the fuel additive). When blended
into a gasoline fuel, the fuel may include about 0.5 ppmw to about 20 ppmw of the
active succinimide detergent, about 1 ppmw to about 10 ppmw, or about 2 ppmw to about
5 ppmw of the succinimide detergent in the fuel (based on total weight of the active
succinimide).
[0040] As discussed more below, the fuel additive and fuels herein include a select weight
ratio of the Mannich detergent to the succinimide detergent.
Alkoxylated Alcohol
[0041] The fuel additives or fuels of the present disclosure may also include one or more
optional alkoxylated alcohols. The alkoxylated alcohol is preferably a polyether prepared
by reacting an long chain alkyl alcohol or alkylphenol with an alkylene oxide. By
one approach, the alkoxylated alcohol may be one or more hydrocarbyl-terminated or
hydrocarbyl-capped poly(oxyalkylene) polymers. The hydrocarbyl moieties thereof may
be aryl or aliphatic groups, and preferably, aliphatic chains that are linear, branched
or cyclic, and most preferably are linear aliphatic chains. In one approach, the alkoxylated
alcohols may have the structure of Formula IIIa, IIIb, and/or IIIc below:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0010)
wherein R
6 of the Formula III structures above is an aryl group or a linear, branched, or cyclic
aliphatic group and preferably having 5 to 50 carbons (or 5 to 30 carbons) or may
be a -C
mH
2m+1 group where m is an integer of 12 or more, R
7 of the Formula III structures above is a C1 to C4 alkyl group, and n is an integer
from 5 to 100 (or as further discussed below).
[0042] In some approaches, suitable alkoxylated alcohols are derived from lower alkylene
oxides selected from the group consisting of ethylene oxide, propylene oxide, butylene
oxide, copolymers thereof, and combinations thereof. Preferably, the lower alkylene
oxides are propylene oxide or butylene oxide or copolymers of ethylene oxide, propylene
oxide, and butylene oxide (as well as any combinations thereof). In another approach,
the alkylene oxides are propylene oxide. Any copolymers of such alkylene oxides may
be random or block copolymers. In one approach, the alkoxylated alcohols may be terminated
or capped with an aryl, alkyl, or hydrocarbyl group and may include one or more aryl
or linear, branched, or cyclic aliphatic C5 to C30 terminated alkoxylated alcohols,
and in other approaches, a C16 to C18 (or blend thereof) terminated alkoxylated alcohol
having 5 to 100, 10 to 80, 20 to 50, or 22 to 32 repeating units of the alkylene oxide
therein (that is, n integer of the formula above). In some approaches, the alkoxylated
alcohols may have a weight average molecular weight of about 1300 to about 2600 and,
in other approaches, about 1600 to about 2200.
[0043] In some approaches, the aliphatic hydrocarbyl terminated alkoxylated alcohols may
include about 20 to about 70 weight percent (in another approach, about 30 to about
50 weight percent) of an aliphatic C16 alkoxylated alcohol having 24 to 32 repeating
units of alkoxylene oxide and/or may include about 80 to about 30 weight percent (in
another approach, about 50 to about 70 weight percent) of an aliphatic C18 alkoxylated
alcohol having 24 to 32 repeating units of alkoxylene oxide. In other approaches,
the fuel additives herein, if including an alkoxylated alcohol, may also have about
8 percent or less (in other approaches, about 6 percent or less, and in yet other
approaches, about 4 percent or less) of C20 or greater alkoxylated alcohols and/or
about 4 weight percent or less (in or other approaches about 2 weight percent or less,
and in yet other approaches, about 1 percent or less) of C14 or lower alkoxylated
alcohols.
[0044] The aryl or hydrocarbyl-capped poly(oxyalkylene) alcohols may be produced by the
addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, or the
butylene oxides, to a desired hydroxy compound R-OH (that is, a starter alcohol) under
polymerization conditions, wherein R is the aryl or hydrocarbyl group having either
5 to 30 carbons or other chain length as noted above and which caps the poly(oxyalkylene)
chain. The alkoxylated alcohols can be prepared by any starter alcohol that provides
the desired polyol distribution. By one approach, the alkoxylated alcohol can be prepared
by reacting a saturated linear or branched alcohol of the desired hydrocarbon size
with the selected alkylene oxide and a double metal or basic catalyst. In one approach,
the alkoxylated alcohol may be nonylphenol alkyxylated alcohol such as nonylphenol
propoxylated alcohol.
[0045] In other approaches, in the polymerization reaction a single type of alkylene oxide
may be employed, e.g., propylene oxide, in which case the product is a homopolymer,
e.g., a poly(oxyalkylene) propanol. However, copolymers are equally satisfactory and
random or block copolymers are readily prepared by contacting the hydroxyl-containing
compound with a mixture of alkylene oxides, such as a mixture of ethylene, propylene,
and/or butylene oxides. Random polymers are more easily prepared when the reactivities
of the oxides are relatively equal. In certain cases, when ethylene oxides is copolymerized
with other oxides, the higher reaction rate of ethylene oxide makes the preparation
of random copolymers difficult. In either case, block copolymers can be prepared.
Block copolymers are prepared by contacting the hydroxyl-containing compound with
first one alkylene oxide, then the others in any order, or repetitively, under polymerization
conditions. In one example, a particular block copolymer may be represented by a polymer
prepared by polymerizing propylene oxide on a suitable monohydroxy compound to form
a poly(oxypropylene) alcohol and then polymerizing butylene oxide on the poly(oxyalkylene)
alcohol.
[0046] A fuel additive or fuel herein, when included, may include about 5 to about 30 weight
percent of the alkoxylated alcohol, about 8 to about 20 weight percent of the alkoxylated
alcohol, or about 10 to about 15 weight percent of the alkoxylated alcohol (based
on the active alkoxylated alcohol in the fuel additive). When blended into a gasoline
fuel, the fuel may include about 2 ppmw to about 150 ppmw of the active alkoxylated
alcohol, about 5 to about 150 ppmw, about 8 ppmw to about 50 ppmw, or about 15 ppmw
to about 40 ppmw of the alkoxylated alcohol in the fuel.
Fuel Additive:
[0047] When formulating the fuel compositions of this application, the above described additives
(including at least the Mannich detergent(s) and the succinimide detergent(s)) may
be employed in amounts sufficient to reduce or inhibit deposit formation in a fuel
system, a combustion chamber of an engine and/or crankcase, and/or within fuel injectors
and within a gasoline direction injection engine and/or a port fuel injection engine.
Such additives may also be provided in amounts to improve injector performance as
described herein. In some aspects, the fuel additive or fuel additive package herein
may include at least the above described Mannich detergent, the succinimide detergent,
and the optional alkoxylated alcohol. The fuel additives herein may also include other
optional additives as needed for a particular application and may include as needed
one or more of a demulsifier, a corrosion inhibitor, an antiwear additive, an antioxidant,
a metal deactivator, an antistatic additive, a dehazer, an antiknock additive, a lubricity
additive, and/or a combustion improver.
[0048] In some approaches or embodiments, the fuel additive or additive package herein may
include about 20 to about 60 weight percent of the Mannich detergent and about 0.5
to about 10 weight percent of the succinimide detergent. In other approaches, the
fuel additive or additive package may also include about 5 to about 30 weight percent
of the alkoxylated alcohol. Other ranges of the Mannich detergent, the succinimide
detergent, and the optional alkoxylated alcohol may also be used in the fuel additive,
the additive package, or the fuel as described above in this disclosure.
[0049] In other approaches, a gasoline fuel composition may include about 40 to about 750
ppmw of the fuel additive or the additive package herein, in other approaches, about
60 to about 380 ppmw, or about 135 to about 310 ppmw of the above noted fuel additive
package and which provides about 15 to about 300 ppmw of the Mannich detergent and
about 0.5 to about 20 ppmw of the succinimide detergent to the fuel (or other ranges
as noted above). In other embodiments, the fuel may also include about 2 to about
90 ppmw of the optional alkoxylated alcohol (or other ranges as noted above). It will
also be appreciated that any endpoint between the above described ranges are also
suitable range amounts as needed for a particular application. The above-described
amounts reflects additives on an active ingredient basis, which means the additives
noted above excludes the weight of (i) unreacted components associated with and remaining
in the product as produced and used, and (ii) solvent(s), if any, used in the manufacture
of the product either during or after its formation.
[0050] In other approaches, the fuel additive package or fuel thereof also has a certain
weight ratio of the alkoxylated alcohol to the Mannich detergent of about 1.0 or less
(i.e., about 1.0:1 or less), about 0.8 or less (i.e., 0.8:1 or less), about 0.6 or
less, about 0.5 or less, about 0.4 or less, or about 0.3 or less, and about 0.1 or
more (i.e., 0.1:1 or more), about 0.2 or more, or about 0.3 or more.
[0051] In yet other approaches, the fuel additive package or fuel thereof may also have
a weight ratio of the Mannich detergent to the succinimide detergent of about 15:1
to about 30:1, or about 20:1 to about 30:1 or about 22:1 to about 30:1 (wherein the
weight ratios are active Mannich detergent to the active succinimide detergent). In
other approaches, the fuel additive package or fuel thereof may have a weight ratio
of the Mannich detergent to the succinimide detergent from about 15:1 to about 25:1,
or from about 20:1 to from about 25:1 (wherein the weight ratios are active Mannich
detergent to the active succinimide detergent). In yet other approaches, the fuel
additive package or fuel thereof may have a weight ratio of the Mannich detergent
to the succinimide detergent from about 25:1 to about 30:1, or from about 26:1 to
about 30:1 (wherein the weight ratios are active Mannich detergent to the active succinimide
detergent). As shown in the Examples below, such weight ratios achieve a surprising
synergy of the detergent additives in engine performance.
Other Additives
[0052] One or more optional compounds may be present in the fuel compositions of the disclosed
embodiments. For example, the fuels may contain conventional quantities of cetane
improvers, octane improvers, corrosion inhibitors, cold flow improvers (CFPP additive),
pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers,
amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat
stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate
ignition accelerators, cyclomatic manganese tricarbonyl compounds, carrier fluids,
and the like. In some aspects, the compositions described herein may contain about
10 weight percent or less, or in other aspects, about 5 weight percent or less, based
on the total weight of the additive concentrate, of one or more of the above optional
additives. Similarly, the fuels may contain suitable amounts of conventional fuel
blending components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and
the like.
[0053] In some aspects of the disclosed embodiments, organic nitrate ignition accelerators
that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic
group is saturated, and that contain up to about 12 carbons may be used. Examples
of organic nitrate ignition accelerators that may be used are methyl nitrate, ethyl
nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl
nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl
nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate,
isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate,
dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate,
cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuranyl
nitrate, and the like. Mixtures of such materials may also be used.
[0054] Examples of suitable optional metal deactivators useful in the compositions of the
present application are disclosed in
U.S. Pat. No. 4,482,357, the disclosure of which is herein incorporated by reference in its entirety. Such
metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene
ethylenediamine, disalicylidene propylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.
[0055] Suitable optional cyclomatic manganese tricarbonyl compounds which may be employed
in the compositions of the present application include, for example, cyclopentadienyl
manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese
tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl. Yet other examples of
suitable cyclomatic manganese tricarbonyl compounds are disclosed in
U.S. Pat. No. 5,575,823 and
U.S. Pat. No. 3,015,668 both of which disclosures are herein incorporated by reference in their entirety.
[0056] Other commercially available detergents may be used in combination with the reaction
products described herein. Such detergents include but are not limited to succinimides,
Mannich base detergents, PIB amine, quaternary ammonium detergents, bis-aminotriazole
detergents as generally described in
U.S. patent application Ser. No. 13/450,638, and a reaction product of a hydrocarbyl substituted dicarboxylic acid, or anhydride
and an aminoguanidine, wherein the reaction product has less than one equivalent of
amino triazole group per molecule as generally described in
U.S. patent application Ser. Nos. 13/240,233 and
13/454,697.
[0057] The additives of the present application and optional additives used in formulating
the fuels of this invention may be blended into the base fuel individually or in various
subcombinations. In some embodiments, the additive components of the present application
may be blended into the fuel concurrently using an additive concentrate, as this takes
advantage of the mutual compatibility and convenience afforded by the combination
of ingredients when in the form of an additive concentrate. Also, use of a concentrate
may reduce blending time and lessen the possibility of blending errors.
Fuels
[0058] The fuels of the present application may be applicable to the operation of diesel,
jet, or gasoline engines, and preferably, spark-ignition or gasoline engines. The
engines may include both stationary engines (e.g., engines used in electrical power
generation installations, in pumping stations, etc.) and ambulatory engines (e.g.,
engines used as prime movers in automobiles, trucks, road-grading equipment, military
vehicles, etc.). For example, the fuels may include any and all middle distillate
fuels, diesel fuels, biorenewable fuels, biodiesel fuel, fatty acid alkyl ester, gas-to-liquid
(GTL) fuels, gasoline, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic
fuels, such as Fischer-Tropsch fuels, liquid petroleum gas, bunker oils, coal to liquid
(CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from
coal (natural, cleaned, and petcoke), genetically engineered biofuels and crops and
extracts therefrom, and natural gas. Preferably, the additives herein are used in
spark-ignition fuels or gasoline. "Biorenewable fuels" as used herein is understood
to mean any fuel which is derived from resources other than petroleum. Such resources
include, but are not limited to, corn, maize, soybeans and other crops; grasses, such
as switchgrass, miscanthus, and hybrid grasses; algae, seaweed, vegetable oils; natural
fats; and mixtures thereof. In an aspect, the biorenewable fuel can comprise monohydroxy
alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples
of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol,
t-butyl alcohol, amyl alcohol, and isoamyl alcohol. Preferred fuels include diesel
fuels.
[0059] Accordingly, aspects of the present application are directed to methods of or the
use of the noted fuel additive package for controlling or reducing fuel injector deposits,
controlling or reducing intake valve deposits, controlling or reducing combustion
chamber deposits, and/or controlling or reducing intake valve sticking in one of port-injection
engines, direct-injection engines, and preferably both engine types. In some approaches,
the fuel additives and fuels herein are configured to reduces deposits when sprayed
from an injector in droplets of about 10 to about 30 microns, when sprayed from an
injector in droplets of about 120 to about 200 microns, or both. As such, the fuel
additives and fuels herein surprisingly provide improved engine performance as defined
herein in both port fuel injected engines (PFI) as well as gasoline direct injection
engines (GDI). In some aspects, the method may also comprise mixing into the fuel
at least one of the optional additional ingredients described above. The improved
engine performance may be evaluated pursuant to the test protocols of ASTM D6201 or
by the methods as set forth in the following two SAE publications:
Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct
Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi: 10.4271/2013-01-2616 and/or
Shanahan, C., Smith, S., and Sears, B., "A General Method for Fouling Injectors in
Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,"
SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271/2017-01-2298, both of which are incorporated herein by reference. Intake valve sticking may be
evaluated using the test protocols at Southwest Research Institute (SWRI, San Antonio
Texas) or similar test house.
[0060] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used
in its ordinary sense, which is well-known to those skilled in the art. Specifically,
it refers to a group having a carbon atom directly attached to the remainder of the
molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group
is independently selected from hydrocarbon substituents, and substituted hydrocarbon
substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups,
mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl
groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon
substituents are present for every ten carbon atoms in the hydrocarbyl group.
[0061] As used herein, the term "percent by weight" or "wt%", unless expressly stated otherwise,
means the percentage the recited component represents to the weight of the entire
composition. All percent numbers herein, unless specified otherwise, is weight percent.
[0062] The term "alkyl" as employed herein refers to straight, branched, cyclic, and/or
substituted saturated chain moieties from about 1 to about 200 carbon atoms. The term
"alkenyl" as employed herein refers to straight, branched, cyclic, and/or substituted
unsaturated chain moieties from about 3 to about 30 carbon atoms. The term "aryl"
as employed herein refers to single and multi-ring aromatic compounds that may include
alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms
including, but not limited to, nitrogen, and oxygen.
[0063] As used herein, the molecular weight is determined by gel permeation chromatography
(GPC) using commercially available polystyrene standards (with a Mp of about 162 to
about 14,000 as the calibration reference). The molecular weight (Mn) for any embodiment
herein may be determined with a gel permeation chromatography (GPC) instrument obtained
from Waters or the like instrument and the data processed with Waters Empower Software
or the like software. The GPC instrument may be equipped with a Waters Separations
Module and Waters Refractive Index detector (or the like optional equipment). The
GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length
of 300×7.5 mm; particle size of 5 µ, and pore size ranging from 100-10000 Å) with
the column temperature at about 40 °C. Un-stabilized HPLC grade tetrahydrofuran (THF)
may be used as solvent, at a flow rate of 0.38 mL/min. The GPC instrument may be calibrated
with commercially available polystyrene (PS) standards having a narrow molecular weight
distribution ranging from 500 - 380,000 g/mol. The calibration curve can be extrapolated
for samples having a mass less than 500 g/mol. Samples and PS standards can be in
dissolved in THF and prepared at concentration of 0.1-0.5 weight percent and used
without filtration. GPC measurements are also described in
US 5,266,223, which is incorporated herein by reference. The GPC method additionally provides
molecular weight distribution information;
see, for example, W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography",
John Wiley and Sons, New York, 1979, also incorporated herein by reference.
[0064] As used herein and unless the context suggests otherwise, a major amount refers to
greater than 50 weight percent (greater than 60 weight percent, greater than 70 weight
percent, greater than 80 weight percent or greater than 90 weight percent), and a
minor amount refers to less than 50 weight percent (less than 40 weight percent, less
than 30 weight percent, less than 20 weight percent, or less than 10 weight percent).
[0065] It is to be understood that throughout the present disclosure, the terms "comprises,"
"includes," "contains," etc. are considered open-ended and include any element, step,
or ingredient not explicitly listed. The phrase "consists essentially of" is meant
to include any expressly listed element, step, or ingredient and any additional elements,
steps, or ingredients that do not materially affect the basic and novel aspects of
the invention. The present disclosure also contemplates that any composition described
using the terms, "comprises," "includes," "contains," is also to be interpreted as
including a disclosure of the same composition "consisting essentially of" or "consisting
of' the specifically listed components thereof.
EXAMPLES
[0066] The following examples are illustrative of exemplary embodiments of the disclosure.
In these examples as well as elsewhere in this application, all ratios, parts, and
percentages are by weight unless otherwise indicated. It is intended that these examples
are being presented for the purpose of illustration only and are not intended to limit
the scope of the invention disclosed herein. The specifications for base fuels A,
B, and C used in the Examples are below in Table 1.
Table 1: Fuel Specifications.
FUEL PROPERTY |
BASE FUEL A |
BASE FUEL B |
BASE FUEL C |
API Gravity |
64.8-50.9 |
60.3 |
58.5 |
Specific Gravity |
0.7207-0.7758 |
0.7377 |
0.7447 |
Density |
0.7200-0.7750 |
0.7370 |
0.7440 |
% Benzene |
<0.8 |
0.47 |
<0.10 |
Bromine No. |
η. a. |
9.7 |
<0.5 |
BTU Gross (btu/lb) |
η. a. |
18711 |
19614 |
BTU Net (btu/lb) |
n.a. |
17477 |
18409 |
Unwashed Gum (ASTM D-381) |
<30 |
3 |
3.5 |
Washed Gum (ASTM D-381) |
<5 |
<0.5 |
<0.5 |
ASTM D-525 Oxidation (minutes) |
<480 |
960 |
960+ |
RVP (ASTM D-5191) |
n.a. |
9.46 |
8.76 |
%Carbon |
n.a |
82.63 |
86.79 |
%Hydrogen |
n.a. |
13.53 |
13.21 |
Aromatics (vol-%) |
<35 |
27.9 |
29.1 |
Olefins (vol-%) |
<15 |
4.7 |
1.2 |
Saturates (vol-%) |
n.a. |
67.4 |
69.7 |
Ethanol (vol-%) |
n.a. |
9.3 |
<0.10 |
Oxygen Content |
<2.7 |
3.84 |
<0.02 |
Sulfur (ppm) |
<10 |
8.4 |
30 |
RON |
89-95 |
98.2 |
97.4 |
MON |
|
87.5 |
89 |
Octane (R+M)/2 |
84-90 |
92.85 |
93.2 |
|
ASTM D-86 (Temperature °F) |
Initial Boiling Point |
η. a. |
87 |
84.6 |
5% |
n.a. |
99.9 |
108 |
10% |
158 |
110.5 |
121.5 |
20% |
n.a. |
125.2 |
104.6 |
30% |
n.a. |
140.3 |
163 |
40% |
n.a. |
152.5 |
191.4 |
50% |
230 |
165.6 |
215.8 |
60% |
n.a. |
228.4 |
228.4 |
70% |
n.a. |
250.5 |
237.3 |
80% |
n.a. |
276 |
254 |
90% |
374 |
316 |
337.5 |
95% |
n.a. |
343.6 |
338.4 |
End Point |
401 |
398.5 |
398.7 |
% Recovery |
η. a. |
96.1 |
97.3 |
Residue |
<2 |
1.1 |
1.1 |
Loss |
η. a. |
2.8 |
1.6 |
EXAMPLE 1
[0067] Inventive and Comparative fuel additive packages of Table 2 below were prepared.
The Mannich detergent was prepared from a high reactivity polyisobutylene cresol,
dibutylamine, and formaldehyde according to a known method (see, e.g.,
US 6,800,103, which is incorporated herein by reference); the propoxylated alcohol was a blend
of commercially available C16-C18 propoxylated alcohols; and the succinimide detergents
were derived from polyisobutylene succinic anhydride (PIBSA) and tetraethylene pentamine
(TEPA) in a 1:1 to 1.6:1 molar ratio, where the polyisobutylene had an about 950 molecular
weight.
Table 2
Ingredients* |
Inventive |
Comparative |
I-1 |
I-2 |
C-1 |
C-2 |
C-3 |
a |
b |
c |
d |
a |
b |
c |
Mannich Detergent, ppmw |
63.8 |
69.1 |
73.4 |
183.4 |
79.6 |
164.1 |
183.4 |
183.4 |
- |
- |
Propoxylated alcohol, ppmw |
19.1 |
20.7 |
22.3 |
55.0 |
23.9 |
49.2 |
55.0 |
55.0 |
55.0 |
55.0 |
Polyisobutenyl mono-succinimide detergent, ppmw |
- |
- |
- |
- |
2.7 |
5.6 |
8.0 |
- |
- |
5.6 |
Polyisobutenyl bis-Succinimide, ppmw |
2.8 |
3.0 |
3.2 |
8.0 |
- |
- |
- |
- |
8.0 |
- |
Mannich detergent to PIBSI ratio |
23.0 |
23.0 |
22.9 |
22.9 |
29.5 |
29.3 |
22.9 |
N/A |
N/A |
N/A |
Alkoxylated alcohol to Mannich detergent ratio |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
- |
- |
* The additive package also contained other non-detergent ingredients, such as demulsifier
and solvent. |
[0068] Each of the additives of Table 2 above were blended into Base Fuel A, B, or C as
specified in the footnotes of Table 3 below. Each fuel was then evaluated for intake
valve deposits and/or injector deposits as set forth in Table 3 below.
Table 3
|
I-1 |
I-2 |
C-1 |
C-2 |
C-3 |
a |
b |
c |
d |
a |
b |
c |
GB/T 19230 ** (M111), IVD, mg |
28 |
14 |
5 |
-- |
-- |
-- |
-- |
-- |
-- |
-- |
ASTM 6201 ** Ford 2.3L, IVD, mg |
-- |
-- |
-- |
-- |
86.9 |
-- |
-- |
-- |
-- |
- |
IVD improvement over average base fuel, % |
88.3 |
94.2 |
97.9 |
-- |
93.1 |
-- |
-- |
-- |
-- |
-- |
GDI by Afton RIFT method***, clean up (CU), % |
-- |
-- |
-- |
59.9 |
-- |
79.9 |
88.0 |
-60.81 |
24.8 |
62.6 |
∗∗ Base fuel IVD: 240 mg for M111 engine in Base Fuel A and 1263 mg for Ford 2.3L engine
in Base Fuel B.
∗∗∗ LHU GDI testing method, refer to the following SAE papers, testing in Base Fuel C:
(1) Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct
Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi:10.4271/2013-01-2616; and/or (2) Shanahan, C., Smith, S., and Sears, B., "A General Method for Fouling Injectors in
Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,"
SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271/2017-01-2298, both of which are incorporated herein by reference.
1No clean-up observed as sample continued a dirty-up phase as shown in FIGS. 1 and
2. |
[0069] In the context of GDI engines, a series of tests were run to evaluate the impact
that the additive packages had on fuel inject deposits in a gasoline direct injection
engine (GDI). All tests were run with a consistent Base Fuel C during a Dirty-up (DU),
Clean-up (CU) and/or Keep Clean (KC) phases of the respective test. The additive packages
of Table 2 above were tested to evaluate the ability of each fuel additive to improve
injector performance by reducing injector deposits in the GDI engine. Results are
shown in Table 3 as well as FIGS. 1 and 2.
[0070] Base fuel C was investigated for a DU level by indirect measurements of injector
fouling, such as by pulse width or long term fuel trim (LTFT), on a gasoline direct
injection GM LHU engine pursuant to the RIFT methods as set forth in
Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct
Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi:10.4271/2013-01-2616 and/or
Shanahan, C., Smith, S., and/or Sears, B., "A General Method for Fouling Injectors
in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,"
SAE Int. J. Fuels Lubr. 10(3):2017, doi: 10.4271/2017-01-2298, both of which are incorporated by reference herein.
[0071] In order to accelerate the DU phase of the Base Fuel, a combination of di-tert-butyl
disulfide (DTBDS, 406 ppmw) and tert-butyl hydrogen peroxide (TBHP, 286 ppmw) were
added to the base fuel and the DU was accelerated to provide the fouling in the range
of 5 to 12%. Percent of fouling is calculated as:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0011)
[0072] GDI clean up (CU) deposit tests were conducted to demonstrate the removal of deposits
that had been formed in the fuel injectors during the dirty-up (DU) phase. The Additive
packages of Table 2 were blended into the Base Fuel C that was used for DU. The test
procedure consisted of a 114 hour cycle at 2000 rpm and 100 Nm torque with continuous
monitoring of injection pulse width to maintain stoichiometric Air/Fuel ratio on the
GM LHU engine. After 66 hours of test operation, the fuel was changed to an additized
formulation that is designed to have a clean-up effect. The percentage of injector
pulse width increase, and subsequent decrease, after completion of the 114 hour cycle
is one parameter for evaluating the fouling or cleaning effect of the fuel candidate.
CU is calculated as in the following equation:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0012)
[0073] As shown in Table 3 above and in FIGS. 1 and 2, Inventive samples with both the Mannich
and succinimide detergents at ratios from 15:1 to 30:1 exhibited improved injector
clean-up relative to the comparative examples with either the Mannich or succinimide
detergents alone. FIG. 1 shows the DU phase (open symbols) and CU phase (closed symbols)
of Comparative additive packages C-1 and C-2 relative to Inventive additive package
I-1d. As shown in Table 3 and FIG. 1, the Comparative sample C-1 with only the Mannich
detergent continued a dirty-up phase in the GDI engine (that is, no clean-up performance),
but Inventive sample I-1d demonstrated improved clean-up with both the Mannich and
the succinimide detergents in the noted ratios. Given that a fuel additive with only
a Mannich detergent (e.g., C-1) had no clean-up performance in a GDI engine (and rather
continued the dirty up phase), Inventive sample I-1d with both the Mannich detergent
and the succinimide detergent demonstrated an unexpected synergy in performance. That
is, it would not have been expected that the clean-up performance with both the succinimide
and the Mannich detergents would have been better than the clean-up performance of
comparative sample C-2 including only the succinimide detergent given that the Mannich
detergent alone provided no clean-up performance (but rather continues DU). Table
3 and FIG. 2 shows a similar pattern of an unexpected synergy with inventive sample
I-2c (both Mannich and succinimide detergents) compared to C-1 (Mannich detergent
only) and C-2 (succinimide detergent only).
[0074] It is noted that, as used in this specification and the appended claims, the singular
forms "a," "an," and "the," include plural referents unless expressly and unequivocally
limited to one referent. Thus, for example, reference to "an antioxidant" includes
two or more different antioxidants. As used herein, the term "include" and its grammatical
variants are intended to be non-limiting, such that recitation of items in a list
is not to the exclusion of other like items that can be substituted or added to the
listed items
[0075] For the purposes of this specification and appended claims, unless otherwise indicated,
all numbers expressing quantities, percentages or proportions, and other numerical
values used in the specification and claims, are to be understood as being modified
in all instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification and attached claims
are approximations that can vary depending upon the desired properties sought to be
obtained by the present disclosure. At the very least, and not as an attempt to limit
the application of the doctrine of equivalents to the scope of the claims, each numerical
parameter should at least be construed in light of the number of reported significant
digits and by applying ordinary rounding techniques.
[0076] It is to be understood that each component, compound, substituent or parameter disclosed
herein is to be interpreted as being disclosed for use alone or in combination with
one or more of each and every other component, compound, substituent or parameter
disclosed herein.
[0077] It is further understood that each range disclosed herein is to be interpreted as
a disclosure of each specific value within the disclosed range that has the same number
of significant digits. Thus, for example, a range from 1 to 4 is to be interpreted
as an express disclosure of the values 1, 2, 3 and 4 as well as any range of such
values.
[0078] It is further understood that each lower limit of each range disclosed herein is
to be interpreted as disclosed in combination with each upper limit of each range
and each specific value within each range disclosed herein for the same component,
compounds, substituent or parameter. Thus, this disclosure to be interpreted as a
disclosure of all ranges derived by combining each lower limit of each range with
each upper limit of each range or with each specific value within each range, or by
combining each upper limit of each range with each specific value within each range.
That is, it is also further understood that any range between the endpoint values
within the broad range is also discussed herein. Thus, a range from 1 to 4 also means
a range from 1 to 3, 1 to 2, 2 to 4, 2 to 3, and so forth.
[0079] Furthermore, specific amounts/values of a component, compound, substituent or parameter
disclosed in the description or an example is to be interpreted as a disclosure of
either a lower or an upper limit of a range and thus can be combined with any other
lower or upper limit of a range or specific amount/value for the same component, compound,
substituent or parameter disclosed elsewhere in the application to form a range for
that component, compound, substituent or parameter.
[0080] The invention further relates to the following numbered embodiments:
- 1. A fuel additive for a spark-ignition engine comprising:
a Mannich detergent including the reaction product of a hydrocarbyl-substituted phenol
or cresol, one or more aldehydes, and one or more amines;
a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating
agent with an amine, polyamine, or alkyl amine having one or more primary, secondary,
or tertiary amino groups; and
wherein a weight ratio of the Mannich detergent to the succinimide detergent is from
about 15:1 to about 30:1.
- 2. The fuel additive of embodiment 1, wherein the weight ratio of the Mannich detergent
to the succinimide detergent is from about 20:1 to about 30:1; and/or wherein the
Mannich detergent has the structure of Formula I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0013)
wherein R1 is hydrogen or a C1 to C4 alkyl group, R2 is a hydrocarbyl group having a molecular weight of about 500 to about 3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl
amino C1-C12 alkyl group.
- 3. The fuel additive of embodiment 2, wherein R2 is polyisobutenyl having a number average molecular weight of about 500 to about
1500.
- 4. The fuel additive of embodiment 1, wherein the succinimide detergent is a hydrocarbyl
substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide
detergent, or a combination thereof; and/or wherein the hydrocarbyl-substituted succinic
acylating agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl
group has a molecular weight of about 450 to about 3000, and wherein a molar ratio
of the hydrocarbyl-substituted succinic anhydride to the amine, polyamine, or alkyl
amine is from about 0.5: 1 to about 2:1.
- 5. The fuel additive of embodiment 4, wherein the hydrocarboyl-substituted succinic
anhydride is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene
has a number average molecular weight of about 500 to about 1200 as measured by GPC
using polystyrene as reference.
- 6. The fuel additive of embodiment 5, wherein the amine, polyamine, or alkyl amine
is tetraethylene pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine or
alkyl amine having the formula H2N-((CHR20-(CH2)q-NH)r-H, wherein R20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q is an integer
of from 1 to 4 and r is an integer of from 1 to 6, and mixtures thereof.
- 7. The fuel additive of embodiment 6, wherein the amine, polyamine, or alkyl amine
is tetraethylene pentamine (TEPA).
- 8. The fuel additive of embodiment 1, further comprising an alkoxylated alcohol, and
wherein a weight ratio of the alkoxylated alcohol to the Mannich detergent is about
1.0 or less; and/or wherein the alkoxylated alcohol is a polyether prepared by reacting
an alkyl alcohol or an alkylphenol with an alkylene oxide selected from ethylene oxide,
propylene oxide, butylene oxide, copolymers thereof, or combinations thereof.
- 9. The fuel additive of embodiment 8, wherein the alkoxylated alcohol is a polyether
having the structure of Formula III:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0014)
wherein R6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group
having 5 to 50 carbons, R7 of Formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100.
- 10. The fuel additive of embodiment 1, wherein the fuel additive includes about 20
to about 60 weight percent of the Mannich detergent, about 0.5 to about 10 weight
percent of the succinimide detergent, and about 5 to about 30 weight percent of an
alkoxylated alcohol.
- 11. A gasoline fuel composition comprising
about 15 to about 300 ppmw of a Mannich detergent including the reaction product of
a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more
amines;
about 0.5 to about 20 ppmw of a succinimide detergent prepared by reacting a hydrocarbyl-substituted
succinic acylating agent with an amine, polyamine, or alkyl amine having one or more
primary, secondary, or tertiary amino groups;
wherein a weight ratio of the Mannich detergent to the succinimide detergent is about
from 15:1 to about 30:1; and
about 5 to about 150 ppmw of an alkoxylated alcohol.
- 12. A method of reducing deposits in a gasoline engine, the method comprising:
operating a gasoline engine on a fuel composition containing a major amount of a gasoline
fuel and a minor amount of a fuel additive by injecting the gasoline fuel through
one or more injectors;
wherein the fuel additive includes (i) a Mannich detergent including the reaction
product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and
one or more amines; (ii) a succinimide detergent prepared by reacting a hydrocarbyl-substituted
succinic acylating agent with an amine, polyamine, or alkyl amine having one or more
primary, secondary, or tertiary amino groups; and (iii) wherein the fuel additive
has a weight ratio of the Mannich detergent to the succinimide detergent of from about
15:1 to about 30:1; and
wherein the fuel additive reduces deposits in the gasoline engine.
- 13. The method of embodiment 12, wherein the fuel additive reduces deposits in a port
fuel injection (PFI) engine, a gasoline direct injection (GDI) engine, or both; and/or
wherein the reduced deposits are reduced injector deposits measured by one of injector
pulse width, injection duration, injector flow, or combinations thereof.
- 14. The method of embodiment 12, wherein the fuel additive reduces deposits when sprayed
from an injector configured to spray droplets of about 10 to about 30 microns, about
120 to about 200 microns, or both.
- 15. The method of embodiment 12, wherein the weight ratio of the Mannich detergent
to the succinimide detergent is from about 20:1 to about 30:1; and/or wherein the
Mannich detergent has the structure of Formula I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0015)
wherein R1 is hydrogen or a C1 to C4 alkyl group, R2 is a hydrocarbyl group having a molecular weight of about 500 to about 3000, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl
amino C1-C12 alkyl group.
- 16. The method of embodiment 12, further comprising an alkoxylated alcohol and
wherein a weight ratio of the alkoxylated alcohol to the Mannich detergent is about
1.0 or less; and/or wherein the alkoxylated alcohol is a polyether prepared by reacting
an alkyl alcohol or an alkylphenol with an alkylene oxide selected from ethylene oxide,
propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; and/or
wherein the fuel additive includes about 20 to about 60 weight percent of the Mannich
detergent, about 0.5 to about 10 weight percent of the succinimide detergent, and
about 5 to about 30 weight percent of the alkoxylated alcohol.
1. A fuel additive for a spark-ignition engine comprising:
a Mannich detergent including the reaction product of a hydrocarbyl-substituted phenol
or cresol, one or more aldehydes, and one or more amines;
a succinimide detergent prepared by reacting a hydrocarbyl-substituted succinic acylating
agent with an amine, polyamine, or alkyl amine having one or more primary, secondary,
or tertiary amino groups; and
wherein a weight ratio of the Mannich detergent to the succinimide detergent is from
about 15:1 to about 30:1.
2. The fuel additive of claim 1, wherein the weight ratio of the Mannich detergent to
the succinimide detergent is from about 20:1 to about 30: 1; and/or wherein the Mannich
detergent has the structure of Formula I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0016)
wherein R
1 is hydrogen or a C1 to C4 alkyl group, R
2 is a hydrocarbyl group having a molecular weight of about 500 to about 3000, R
3 is a C1 to C4 alkylene or alkenyl group, and R
4 and R
5 are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl
amino C1-C12 alkyl group.
3. The fuel additive of claim 2, wherein R2 is polyisobutenyl having a number average molecular weight of about 500 to about
1500 as measured by GPC using polystyrene as reference.
4. The fuel additive of any one of claims 1 to 3, wherein the succinimide detergent is
a hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted bis-succinimide
detergent, or a combination thereof; and/or wherein the hydrocarbyl-substituted succinic
acylating agent is a hydrocarbyl-substituted succinic anhydride, wherein the hydrocarbyl
group has a number average molecular weight of about 450 to about 3000 as measured
by GPC using polystyrene as reference, and wherein a molar ratio of the hydrocarbyl-substituted
succinic anhydride to the amine, polyamine, or alkyl amine is from about 0.5: 1 to
about 2:1.
5. The fuel additive of claim 4, wherein the hydrocarboyl-substituted succinic anhydride
is polyisobutylene substituted succinic anhydride, and wherein the polyisobutylene
has a number average molecular weight of about 500 to about 1200 as measured by GPC
using polystyrene as reference.
6. The fuel additive of claim 5, wherein the amine, polyamine, or alkyl amine is tetraethylene
pentamine (TEPA), triethylenetetraamine (TETA), or a polyamine or alkyl amine having
the formula H2N-((CHR20-(CH2)q-NH)r-H, wherein R20 thereof is hydrogen or an alkyl group having from 1 to 4 carbon atoms, q is an integer
of from 1 to 4 and r is an integer of from 1 to 6, and mixtures thereof.
7. The fuel additive of claim 6, wherein the amine, polyamine, or alkyl amine is tetraethylene
pentamine (TEPA).
8. The fuel additive of any one of claims 1 to 7, further comprising an alkoxylated alcohol,
and wherein a weight ratio of the alkoxylated alcohol to the Mannich detergent is
about 1.0 or less; and/or wherein the alkoxylated alcohol is a polyether prepared
by reacting an alkyl alcohol or an alkylphenol with an alkylene oxide selected from
ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations
thereof.
9. The fuel additive of claim 8, wherein the alkoxylated alcohol is a polyether having
the structure of Formula III:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0017)
wherein R
6 of Formula III is an aryl group or a linear, branched, or cyclic aliphatic group
having 5 to 50 carbons, R
7 of Formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100.
10. The fuel additive of any one of claims 1 to 9, wherein the fuel additive includes
about 20 to about 60 weight percent of the Mannich detergent, about 0.5 to about 10
weight percent of the succinimide detergent, and about 5 to about 30 weight percent
of an alkoxylated alcohol.
11. A gasoline fuel composition comprising a fuel additive of any one of claims 1 to 10,
the composition comprising
about 15 to about 300 ppmw of the Mannich detergent including the reaction product
of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more
amines;
about 0.5 to about 20 ppmw of the succinimide detergent prepared by reacting a hydrocarbyl-substituted
succinic acylating agent with an amine, polyamine, or alkyl amine having one or more
primary, secondary, or tertiary amino groups;
wherein a weight ratio of the Mannich detergent to the succinimide detergent is about
from 15:1 to about 30:1; and
about 5 to about 150 ppmw of the alkoxylated alcohol.
12. A method of reducing deposits in a gasoline engine, the method comprising:
operating a gasoline engine on a fuel composition according to claim 11 or on a fuel
composition containing a major amount of a gasoline fuel and a minor amount of a fuel
additive by injecting the gasoline fuel through one or more injectors;
wherein the fuel additive includes (i) a Mannich detergent including the reaction
product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and
one or more amines; (ii) a succinimide detergent prepared by reacting a hydrocarbyl-substituted
succinic acylating agent with an amine, polyamine, or alkyl amine having one or more
primary, secondary, or tertiary amino groups; and (iii) wherein the fuel additive
has a weight ratio of the Mannich detergent to the succinimide detergent of from about
15:1 to about 30:1; and
wherein the fuel additive reduces deposits in the gasoline engine.
13. The method of claim 12, wherein the fuel additive reduces deposits in a port fuel
injection (PFI) engine, a gasoline direct injection (GDI) engine, or both; and/or
wherein the reduced deposits are reduced injector deposits measured by one of injector
pulse width, injection duration, injector flow, or combinations thereof.
14. The method of claim 12 or 13, wherein the fuel additive reduces deposits when sprayed
from an injector configured to spray droplets of about 10 to about 30 microns, about
120 to about 200 microns, or both.
15. The method of any one of claims 12 to 14, wherein the weight ratio of the Mannich
detergent to the succinimide detergent is from about 20:1 to about 30:1; and/or wherein
the Mannich detergent has the structure of Formula I:
![](https://data.epo.org/publication-server/image?imagePath=2024/14/DOC/EPNWA1/EP23195793NWA1/imgb0018)
wherein R
1 is hydrogen or a C1 to C4 alkyl group, R
2 is a hydrocarbyl group having a molecular weight of about 500 to about 3000, R
3 is a C1 to C4 alkylene or alkenyl group, and R
4 and R
5 are, independently, hydrogen, a C1 to C12 alkyl group, or a mono or di(C1 to C4)alkyl
amino C1-C12 alkyl group.
16. The method of any one of claims 12 to 15, further comprising an alkoxylated alcohol
and wherein a weight ratio of the alkoxylated alcohol to the Mannich detergent is
about 1.0 or less; and/or wherein the alkoxylated alcohol is a polyether prepared
by reacting an alkyl alcohol or an alkylphenol with an alkylene oxide selected from
ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations
thereof; and/or wherein the fuel additive includes about 20 to about 60 weight percent
of the Mannich detergent, about 0.5 to about 10 weight percent of the succinimide
detergent, and about 5 to about 30 weight percent of the alkoxylated alcohol.