Note: Descriptions are shown in the official language in which they were submitted.
GASOLINE ADDITIVE COMPOSITION FOR IMPROVED ENGINE
PERFORMANCE
TECHNICAL FIELD
[0001] This disclosure is directed to fuel additives for spark-ignition
engines providing
enhanced engine and/or injector performance, to fuel compositions including
such
additives, and to methods for using such fuel additives in a fuel composition.
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 do not necessarily provide comparable performance
in gasoline
direct injection engines 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
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CA 3211252 2023-09-06
other fuel additives tend to be expensive and/or difficult to manufacture or
incorporate in
fuels. Such shortcomings are particularly true in the context of quaternary
ammonium salt
fuel additives that are often difficult or costly to manufacture and/or
require relatively high
treat rates for performance.
SUMMARY
[0004] In one aspect, a method of providing improved engine performance
is provided
herein. In one embodiment or approach, a fuel additive package for a spark-
ignition
engine is described herein to provide the improved engine performance and
includes (i) a
Mannich detergent including the reaction product of a hydrocarbyl-substituted
phenol, one
or more aldehydes, and one or more amines and (ii) a quaternary ammonium
internal salt
obtained from amines or polyamines that is substantially devoid of any free
anion species.
[0005] In other approaches or embodiments, the fuel additive package
described above
may include one or more optional features or embodiments in any combination.
These
optional features or embodiments may include one or more of the following:
wherein the
fuel additive package further includes an alkoxylated alcohol; and/or wherein
a weight
ratio of the alkoxylated alcohol to the Mannich detergent is about 0.8 or
less; and/or
wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl
alcohol or an
allcylphenol with an alkylene oxide selected from ethylene oxide, propylene
oxide,
butylene oxide, copolymers thereof, or combinations thereof; and/or wherein a
weight ratio
of the Mannich detergent to the quaternary ammonium internal salt is about 5:1
to about
100:1; and/or wherein the Mannich detergent has the structure of Formula I:
OH
R1 40 R3 R4
\N/
R5
R2 (Formula I)
wherein R1 is hydrogen or a Cl to C4 alkyl group, R2 is a hydrocarbyl group
having a
number average molecular weight of about 500 to about 3000, R3 is a Cl to C4
alkylene or
2
CA 3211252 2023-09-06
1 5
alkenyl group, and R4 and R5 are, independently, hydrogen, a Cl to C12 alkyl
group, or a
Cl to C4 alkyl amino C1-C12 alkyl group; and/or wherein the quaternary
ammonium
internal salt has the structure of Formula II
0
R9
R R.
R8
R10 R9 0 (Formula II)
wherein Rand R' are, independently, alkylene linkers having 1 to 10 carbon
atoms; R8 is a
C12 to C100 alkylene, alkene, or hydrocarbyl group or an aryl group or
optionally
substituted aryl group; each R9 is, independently, a linear or branched Cl to
C4 alkyl
group; and Rio is a hydrogen atom or a Cl to C4 alkyl group; and/or wherein
the
alkoxylated alcohol is a polyether having the structure of Formula III:
R7
Re OH
n (Formula III)
wherein R6 is an aryl group or a linear, branched, or cyclic aliphatic group
having 5 to 50
carbons, R7 is a Cl to C4 alkyl group, and n is an integer from 5 to 100;
and/or wherein the
fuel additive package includes about 20 to about 60 weight percent of the
Mannich
detergent, about 1 to about 15 weight percent of the quaternary ammonium
internal salt,
and about 5 to about 30 weight percent of the alkoxylated alcohol; and/or
further
comprising 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/or wherein the fuel additive
package
includes about 0.1 to about 10 weight percent of the succinimide detergent;
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 further
comprising 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
3
CA 3211252 2023-09-06
lubricity additive, and/or a combustion improver.
[0006] In other approaches or embodiments, the disclosure herein also
describes a
gasoline fuel composition comprising about 40 to about 750 ppmw of a fuel
additive
package as described in any of the embodiments from the previous two
paragraphs and
including about 15 to about 300 ppmw of the Mannich detergent, about 0.1 to
about 10
ppmw of the quaternary ammonium internal salt, and about 2 to about 90 ppmw of
the
alkoxylated alcohol.
[0007] The gasoline fuel composition of the previous paragraph may also
include other
optional features or embodiments in any combination. These optional feature or
embodiments of the gasoline fuel composition may include one or more of the
following:
wherein intake valve deposits, as measured pursuant to one of ASTNI D6201, or
ASTM
D5500 are reduced when the gasoline fuel composition is combusted in a spark-
ignition
engine as compared to combusting a gasoline fuel composition including the
aminophenol
detergent and/or the alkoxylated alcohol and being devoid of the quaternary
ammonium
internal salt; and/or wherein the spark-ignition engine is a gasoline direct
or port fuel
injection engine.
[0008] In yet other approaches or embodiments, a method of improving the
injector
performance of a gasoline direct injection (GDI) engine is described herein.
The method
includes operating the gasoline direct injection engine on a fuel composition
containing a
major amount of a gasoline fuel and a minor amount of the fuel additive
package as
described by any embodiment set forth in this Summary, and wherein the fuel
additive
package in the gasoline fuel improves the injector performance of the gasoline
direct
injection engine. Also provided herein is the use of a fuel additive package
as described by
any embodiment herein or any embodiment of a fuel composition herein for
improving the
injector performance of a gasoline direct injection engine.
[0009] The method or the use of the previous paragraph may include
optional steps,
features, or limitations in any combination thereof. Approaches or embodiments
of the
method or use may include one or more of the following: wherein the improved
injector
performance is one of improved fuel flow, improved fuel economy, improved
engine
efficiency, or combinations thereof; and/or wherein the improved injector
performance is
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CA 3211252 2023-09-06
measured by one of injector pulse width, injection duration, injector flow, or
combinations
thereof.
BRIEF DESCRIPTION OF DRAWING FIGURES
[00010] FIG. 1 is a graph showing percent of injector fouling in a base fuel
and an
additized fuel;
[00011] FIG. 2 is a graph showing Long Term Fuel Trim (LTFT) of a base fuel
and an
additized fuel; and
[00012] FIG. 3 is a graph showing Long Term Fuel Trim (LTFT) of Inventive 5
and
Comparatives 3 and 4.
DETAILED DESCRIPTION
[00013] The present disclosure provides fuel additives including
combinations of
Mannich detergents and quaternary ammonium salts and, in particular, Mannich
detergents
and hydrocarbyl-substituted quaternary ammonium internal salts discovered
effective 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 the improved engine
and/or
injector performance.
[00014] In aspects or embodiments of this disclosure, improved engine 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. 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.
[00015] Mannich Detergent
[00016] In one aspect, the fuel additives and fuels herein include a
Mannich detergent.
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CA 3211252 2023-09-06
Suitable Mannich detergents include the reaction product(s) of an alkyl-
substituted
hydroxyaromatic or phenol compound, aldehyde, and amine as discussed more
below.
[00017] 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 4 or about 1 to about 2) as determined by GPC
using
polystyrene as reference.
[00018] 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 100 C. Acidic catalysts are generally used to
promote
.. Friedel-Crafts alkylation. Typical catalysts used in commercial production
include
sulphuric acid, BF3, aluminum phenoxide, methanesulphonic acid, cationic
exchange resin,
acidic clays and modified zeolites.
[00019] 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.
[00020] Polybutylene is preferred for forming the hydrocarbyl-substituted
hydroxyaromatic or phenol compounds herein. Unless otherwise specified herein,
the term
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CA 3211252 2023-09-06
"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
BF3
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.
[00021] 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.
[00022] 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
7
CA 3211252 2023-09-06
groups.
[00023] 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 H2N--(A-NH--)1-1, 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.
[00024] 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,1\11,N",Nw-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.
8
CA 3211252 2023-09-06
Exemplary amines may include N,N-dimethy1-1,3-propanediamine and/or N-methyl
piperazine.
[00025] 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-methy1-1,2-ethanediamine, N-(tert-buty1)-1-
methy1-1,3-
propane diamine, and 3,5-di(tert-butyl)aminoethylpiperazine.
[00026] 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.
[00027] 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.
[00028] In other approaches or embodiments, suitable Mannich detergents for
the fuel
additives herein may have a structure of Formula I below:
9
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OH
R1 R3 R4
\N/
R5
R2 (Formula I)
wherein RI is hydrogen or a Cl to C4 alkyl group, R2 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), R3 is a Cl to C4 alkylene or alkenyl linking
group, and R4 and
R5 are, independently, hydrogen, a Cl to C12 alkyl group, or a Cl to C4 alkyl
amino Cl-
C12 alkyl group.
[00029] A fuel additive or additive package may include about 10 to about 70
weight
percent of the above-described Mannich detergent, about 20 to about 60 weight
percent of
the Mannich detergent, or about 30 to about 50 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).
[00030] Quaternary Ammonium Internal Salt:
[00031] In another aspect, the fuel additives or fuels herein include a
quaternary
ammonium salt and, preferably, a quaternary ammonium internal salt or betaine
compound. In approaches or embodiments, the quaternary ammonium salt additive
may
be any hydrocarbyl substituted quaternary ammonium internal salt (or betaine)
obtained
from amines or polyamines that are substantially devoid of any free anion
species. For
example, such additive may be made by reacting a,tertiary amine of the
structure below
R N R
CA 3211252 2023-09-06
wherein each R group of the above structure is independently selected from
hydrocarbyl
groups containing from 1 to 200 carbon atoms with a halogen substituted C2-C8
carboxylic acid, ester, amide, or salt thereof. In approaches, what is
generally to be
avoided is quaternizing agents selected from the group consisting of
hydrocarbyl
substituted carboxylates, carbonates, cyclic-carbonates, phenates, epoxides,
or mixtures
thereof. In one embodiment, the halogen substituted C2-C8 carboxylic acid,
ester, amide,
or salt thereof may be selected from chloro-, bromo-, fluoro-, and iodo-C2-C8
carboxylic
acids, esters, amides, and salts thereof. The salts may be alkali or alkaline
earth metal salts
selected from sodium, potassium, lithium calcium, and magnesium salts. A
particularly
useful halogen substituted compound for use in the reaction is the sodium or
potassium salt
of a chloroacetic acid.
[00032] As used herein the term "substantially devoid of free anion species"
means that
the anions, for the most part are covalently bound to the product such that
the reaction
product as made does not contain substantial amounts of free anions or anions
that are
ionically bound to the product. In one embodiment, "substantially devoid"
means a range
from 0 to less than about 2 weight percent of free anion species, less than
about 1.5 weight
percent, less than about 1 weight percent, less than about 0.5 weight percent,
or none.
[00033] In another approach or embodiment, a tertiary amine including
monoamines
and polyamines may be reacted with the halogen substituted acetic acid, ester,
or other
derivative thereof to provide the quaternary ammonium internal salt additive
herein.
Suitable tertiary amine compounds are those of structure above wherein each of
R group is
independently selected, as noted above, from hydrocarbyl groups containing
from 1 to 200
carbon atoms. Each hydrocarbyl group R may independently be linear, branched,
substituted, cyclic, saturated, unsaturated, or contain one or more hetero
atoms. Suitable
hydrocarbyl groups may include, but are not limited to alkyl groups, aryl
groups, alkylaryl
groups, arylalkyl groups, alkoxy groups, aryloxy groups, amido groups, ester
groups,
imido groups, and the like. Any of the foregoing hydrocarbyl groups may also
contain
hetero atoms, such as oxygen or nitrogen atoms. Particularly suitable
hydrocarbyl groups
may be linear or branched alkyl groups. In some approaches, the tertiary amine
may be the
reaction product of a diamine or triamine with one tertiary amine and a
hydrocarbyl
11
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substituted carboxylic acid. In other approaches, some representative examples
of amine
reactants which can be reacted to yield compounds of this disclosure include,
but are not
limited to, trimethyl amine, triethyl amine, tri-n-propyl amine, dimethylethyl
amine,
dimethyl lauryl amine, dimethyl oleyl amine, dimethyl stearyl amine, dimethyl
eicosyl
amine, dimethyl octadecyl amine, N,N-dimethylpropane diamine, N-methyl
piperidine,
N,N'-dimethyl piperazine, N-methyl-N-ethyl piperazine, N-methyl morpholine, N-
ethyl
morpholine, N-hydroxyethyl morpholine, pyridine, triethanol amine,
triisopropanol amine,
methyl diethanol amine, dimethyl ethanol amine, lauryl diisopropanol amine,
stearyl
diethanol amine, dioleyl ethanol amine, dimethyl isobutanol amine, methyl
diisooctanol
amine, dimethyl propenyl amine, dimethyl butenyl amine, dimethyl octenyl
amine, ethyl
didodecenyl amine, dibutyl eicosenyl amine, triethylene diamine, hexa-
methylenetetramine, N,N,M,N1-tetramethylethylenediamine, N,N,N',N'-tetramethyl-
propylenediamine, N,N,N1,Nr-tetraethyl-1,3-propanediamine, methyldi-cyclohexyl
amine,
2,6-dimethylpyridine, dimethylcylohexylamine, C10-C30-alkyl or alkenyl-
substituted
amidopropyldimethylamine, C12-C200-alkyl or alkenyl-substituted succinic-
carbonyl-
dimethylamine, and the like. In one approach or embodiment, a suitable
quaternary
ammonium internal salt additive may be the internal salts of oleyl amidopropyl
dimethylamino or ()ley' dimethyl amine.
[00034] If the amine contains solely primary or secondary amino groups, it may
be
necessary to alkylate at least one of the primary or secondary amino groups to
a tertiary
amino group prior to the reaction with the halogen substituted C2-C8
carboxylic acid,
ester, amide, or salt thereof. In one embodiment, alkylation of primary amines
and
secondary amines or mixtures with tertiary amines may be exhaustively or
partially
alkylated to a tertiary amine. It may also be necessary to properly account
for the
hydrogens on the nitrogen and provide base or acid as required (e.g.,
alkylation up to the
tertiary amine requires removal (neutralization) of the hydrogen (proton) from
the product
of the alkylation). If alkylating agents, such as, alkyl halides or dialkyl
sulfates are used,
the product of alkylation of a primary or secondary amine is a protonated salt
and needs a
source of base to free the amine for further reaction.
[00035] The halogen substituted C2-C8 carboxylic acid, ester, amide, or salt
thereof for
12
CA 3211252 2023-09-06
use in making the quaternary internal salt additive may be derived from a mono-
, di-, or tri-
chloro-, bromo-, fluoro-, or iodo-carboxylic acid, ester, amide, or salt
thereof selected from
the group consisting of halogen-substituted acetic acid, propanoic acid,
butanoic acid,
isopropanoic acid, isobutanoic acid, tert-butanoic acid, pentanoic acid,
heptanoic acid,
octanoic acid, halo-methyl benzoic acid, and isomers, esters, amides, and
salts thereof.
The salts of the carboxylic acids may include the alkali or alkaline earth
metal salts, or
ammonium salts including, but not limited to the Na, Li, K, Ca, Mg, triethyl
ammonium
and triethanol ammonium salts of the halogen-substituted carboxylic acids. A
particularly
suitable halogen substituted carboxylic acid, ester, or salt thereof may be
selected from
chloroacetic acid or esters thereof and sodium or potassium chloroacetate. The
amount of
halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof
relative to the
amount of tertiary amine reactant may range from a molar ratio of about 1:0.1
to about
0.1:1Ø
[00036] In yet other approaches, internal salts of the mixtures herein may be
made
according to the foregoing procedures and may include, but are not limited to
(1)
hydrocarbyl substituted compounds of the formula R"-NMe2CH2C00 where R" is
from
Cl to C30 or a substituted amido group; (2) fatty amide substituted internal
salts; and (3)
hydrocarbyl substituted imide, amide, or ester internal salts wherein the
hydrocarbyl group
has 8 to 40 carbon atoms. Particularly suitable internal salts may be selected
from the
group consisting of polyisobutenyl substituted succinimide, succinic diamide,
and succinic
diester internal salts; C8-C40 alkenyl substituted succinimide, succinic
diamide, and
succinic diester internal salts; oleyl amidopropyl dimethylamino internal
salts; and oleyl
dimethylamino internal salts.
[00037] In yet another approach, the quaternary ammonium internal salt of the
fuel
additives and fuels herein is an internal salt or betaine compound having the
structure of
Formula II below:
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=
0
R9
8
R8
Rio R9 0 (Formula II)
wherein Rand R' of the structure above are independently alkylene linkers
having 1 to 10
carbon atoms (in other approaches 1 to 3 carbon atoms); R8 is a saturated
alkylene,
unsaturated alkene, or a linear, branched, or cyclic hydrocarbyl group or
optionally a
substituted or unsubstituted C12 to C100 hydrocarbyl group, or an aryl group
or optionally
substituted aryl group (in one approach, R8 is a C8 to C20 hydrocarbyl group);
each R9 is
independently a linear or branched Cl to C4 alkyl group; and Rio is a hydrogen
atom or a
Cl to C4 alkyl group. The internal salts of Formula II may also be
substantially devoid of
free anion species as discussed above.
[00038] In another approach, the quaternary ammonium salt additive includes
the
compound of Formula II above wherein R is a propylene linker, R' is a
methylene linker,
R8 is a C8 to C20 hydrocarbyl group, each R9 is a methyl group, and Rio is
hydrogen. In
yet other approaches, the quaternary ammonium salt internal salt is selected
from oleyl
amidopropyl dimethylamine internal salts or oleyl dimethylamino internal
salts. In some
approaches, such additive may be substantially devoid of free anion species as
noted
above.
[000391 An exemplary reaction scheme of preparing the quaternary ammonium
internal
salt is shown below in the exemplary process of Reaction Scheme I; of course,
other
methods of preparing the first quaternary ammonium salt additives described
herein may
also be utilized:
R9
H2N R9
R9
R8 OH
R9
R9
14
CA 3211252 2023-09-06
0
R
N/
R8 g
Rg
0
KOH CI
R'
0
0
Rg
NR I e
R8
R9
In the reaction scheme above, R8 may be as described above or, in one
approach, an alkyl
group such as a Cl2 to C100 hydrocarbyl group; R and R' are independently
allcylene
linkers having 1 to 10 carbon atoms; each R9 is independently a alkyl group or
a linear or
branched CI to C4 group; and R"' is an alkyl group or hydrogen.
[00040] A fuel additive herein may include about 1 to about 15 weight percent
of the
quaternary ammonium internal salt, about 1 to about 10 weight percent of the
quaternary
ammonium internal salt, or about 1.5 to about 5 weight percent of the
quaternary
ammonium internal salt (based on the total active weight of the quaternary
ammonium salt
in the fuel additive). When blended into a gasoline fuel, the fuel may include
about about
0.1 to about 20 ppmw of the active quaternary ammonium internal salt, about
0.1 to about
10 ppmw, about 0.3 ppmw to about 5 ppmw, or about 1 ppmw to about 3 ppmw of
the
active quaternary ammonium internal salt in the fuel.
[00041] Alkoxylated Alcohol
[00042] 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
CA 3211252 2023-09-06
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 Ma, IIIb, and/or IIIc below:
R
R 77
R6 OOH
OH 0
n
n
R7
(Formula IIIa) (Formula II%)
H3C
R7
H3C
OH
H3C
-
CH3
(Formula Mc)
wherein R6 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 -CmHzimpi group where
m is an
integer of 12 or more, R7 is a Cl to C4 alkyl group, and n is an integer from
5 to 100 (or as
further discussed below).
[00043] 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
16
CA 3211252 2023-09-06
other approaches, about 1600 to about 2200.
[00044] 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.
[00045] 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.
[00046] 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
17
CA 3211252 2023-09-06
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 mono-
hydroxy compound to form a poly(oxypropylene) alcohol and then polymerizing
butylene
oxide on the poly(oxyalkylene) alcohol.
[00047] 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, 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.
[00048] Succinimide Detergents
[00049] The fuel additives or fuels herein may also include one or more
optional
hydrocarbyl substituted dicarboxylic anhydride derivatives, and preferably one
or more
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
detergents may be mono-succinimides, bis-succinimides, or combinations thereof
[00050] In some approaches or embodiments, the hydrocarbyl substituted
dicarboxylic
anhydride derivative may include a hydrocarbyl substituent having a number
average
molecular weight ranging from about 450 to about 3000 as measured by GPC using
18
CA 3211252 2023-09-06
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 H2N¨((CHR1¨(CH2)q¨NH)r¨H, wherein RI 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.
[00051] In other approaches, the hydrocarbyl substituted dicarboxylic
anhydride may be
a hydrocarbyl carbonyl compound of the Formula IV:
(Formula IV)
where Rio is a hydrocarbyl group derived from a polyolefin. In some aspects,
the
hydrocarbyl carbonyl compound may be a polyalkylene succinic anhydride
reactant
wherein Rio 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 Rio
may range from about 600 to about 2500, or from about 700 to about 1500, as
measured by
GPC using polystyrene as reference. A particularly useful Rio has a number
average
molecular weight of about 950 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.
19
CA 3211252 2023-09-06
[00052] The Rio hydrocarbyl moiety 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 Rio 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 Rio
polyalkenyl radicals may be formed by any suitable methods, such as by
conventional
catalytic oligomerization of alkenes.
[00053] In some aspects, high reactivity polyisobutenes having relatively
high
proportions of polymer molecules with a terminal vinylidene group may be used
to form
the Rio 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.
[00054] 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.
[00055] 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.
CA 3211252 2023-09-06
[00056] 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,ethanediy1) bis-1,3- propanediamine. A
particularly
useful ethylene polyamine is a compound of the formula H2N¨((CHRI¨(CH2)q¨NH),--
-
H, wherein Ri is hydrogen, q is 1 and r is 4.
[00057] In yet further approaches, the hydrocarbyl substituted dicarboxylic
anhydride
derivative is a compound of Formula V
0
R10
N¨R11
o (Formula V)
wherein Rio is a hydrocarbyl group (such as polyisobutylene and/or the other
above
described Rio moieties) and Ru is a hydrogen, an alkyl group, an aryl group, -
OH, -NHR12,
or a polyamine, or an alkyl group containing one or more primary, secondary,
or tertiary
amino groups. In some approaches, Ru is derived from ethylene diamine,
diethyelene
triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene
hexamine, N,N'-
(iminodi-2,1,ethanediyObis-1,3-propanediamine and combinations thereof. In
some
embodiments, Rio is a hydrocarbyl group and Ri is hydrogen, an alkyl group, an
aryl
group, -OH, -NHR12, or a polyamine and wherein R12 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,ethanediy1)bis-1,3-
propanediamine and combinations thereof. In still other embodiments, R4 in the
compound of Formula I is a hydrocarbyl group having a number average molecular
weight
from about 450 to about 3,000 and Rii is derived from tetraethylene pentamine
and
derivatives thereof
[00058] In yet other approaches Rii is a compound of Formula VI
21
CA 3211252 2023-09-06
(( CH2+ A )( CH2+NR13R14
m nP (Formula VI)
wherein A is NR12 or an oxygen atom, R12, R13, and R14 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, RI3 and R14 of Formula VI, together with the nitrogen atom
to which
.. they are attached, form a 5 membered ring. In approaches, the succinimide
detergent is a
hydrocarbyl substituted mono-succinimide detergent, a hydrocarbyl substituted
bis-
succinimide detergent, or a combination thereof
[00059] A fuel additive or fuel herein, when included, may include about 0.1
to about
weight percent of the active succinimide detergent, about 0.5 to about 8
weight percent
10 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.
.. [00060] Fuel Additive:
[00061] When formulating the fuel compositions of this application, the above
described additives (including at least the Mannich detergent and quaternary
ammonium
internal salt) 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 quaternary
ammonium internal
salt, an optional alkoxylated alcohol, and an optional succinimide detergent.
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.
[00062] In some approaches or embodiments, the fuel additive or additive
package
22
CA 3211252 2023-09-06
herein may include about 30 to about 60 weight percent of the Mannich
detergent and
about 1 to about 15 weight percent of the quaternary ammonium internal salt.
In other
approaches, the fuel additive or additive package may also include about 5 to
about 20
weight percent of the alkoxylated alcohol and/or about 0.1 to about 10 weight
percent of
the Succinimide detergent.
[00063] In other approaches, a gasoline fuel composition may include about 40
to about
750 ppmw of the fuel additive or 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 0.1 to about 10 ppmw of the quaternary ammonium internal salt to the
fuel. In other
embodiments, the fuel may also include about 2 to about 90 ppmw of the
alkoxylated
alcohol and/or about 0.5 to about 20 ppmw of the succinimide detergent. 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.
[00064] 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 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), about 0.2 or more, or about 0.3 or more. In
yet other
approaches, the fuel additive package or fuel thereof may also have a weight
ratio of the
Mannich detergent to the quaternary ammonium internal salt of about 5:1 to
about 100:1 or
about 20:1 to about 80:1 or about 30:1 to about 75:1 (wherein the weight
ratios are active
Mannich detergent to the active quaternary ammonium internal salt).
[00065] Other Additives
[00066] 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
23
CA 3211252 2023-09-06
=
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.
[00067] 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.
[00068] 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.
[00069] 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
24
CA 3211252 2023-09-06
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.
[00070] 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.
[00071] 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 sub-combinations. 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.
[00072] Fuels
[00073] 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
CA 3211252 2023-09-06
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.
[00074] 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
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.
[00075] 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,
26
CA 3211252 2023-09-06
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.
[00076] 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.
[00077] 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.
[00078] 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 300x7.5 mm; particle size of 5 , and pore size ranging
from 100-
10000 A) 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/m in.
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
27
CA 3211252 2023-09-06
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.
[00079] 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
[00080] 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 shown below in Table 1.
[00081] Table 1: Fuel Specifications.
FUEL PROPERTY BASE FUEL A BASE FUEL B BASE FUEL C
API Gravity 60.3 58.5 58.7
Specific Gravity 0.7377 0.7447 0.7440
Density 0.7370 0.7440 0.7432
% Benzene 0.47 <0.10 n.a.
Bromine No. 9.7 <0.5 n.a.
BTU Gross (btu/lb) 18711 19614 19674
BTU Net (btu/lb) 17477 18409 18465
28
CA 3211252 2023-09-06
,
i .
Unwashed Gum
3 3.5 1.5
(ASTM D-381)
Washed Gum (ASTM
<0.5 <0.5 <0.5
D-381)
ASTM D-525
960 960+ 960+
Oxidation (minutes)
RVP (ASTM D-5191) 9.46 8.76 8.8
%Carbon 82.63 86.79 n.a.
%Hydrogen 13.53 13.21 n.a.
Aromatics (vol-%) 27.9 29.1 30.7
Olefins (vol-%) 4.7 1.2 9.2
Saturates (vol-%) 67.4 69.7 60.1
Ethanol (vol-%) 9.3 <0.10 n.a.
Oxygen Content 3.84 <0.02 0
Sulfur (ppm) 8.4 30 4.6
RON 98.2 97.4 91.4
MON 87.5 89 83.3
Octane (R+M)/2 92.85 93.2 87.35
ASTM D-86 (Temperature F)
Initial Boiling Point 87 84.6 91.3
5% 99.9 108 113.7
10% 110.5 121.5 125
20% 125.2 104.6 140.2
30% 140.3 163 157.1
40% 152.5 191.4 174.2
50% 165.6 215.8 193.3
60% 228.4 228.4 227.1
70% 250.5 237.3 257.8
80% 276 254 288.5
90% 316 337.5 332.6
95% 343.6 338.4 368.4
End Point 398.5 398.7 423.8
% Recovery 96.1 97.3 97.2
Residue 1.1 1.1 1.1
Loss 2.8 1.6 1.7
29
CA 3211252 2023-09-06
[00082] EXAMPLE 1
[00083] An oleylamidopropyl dimethylammonium betaine quaternary ammonium
internal salt can be made by the process described in US Patent No. 8,894,726
(Inventive
Example 3), which is incorporated herein by reference.
[00084] EXAMPLE 2
[00085] Inventive and comparative fuel additive packages of Table 2 below were
prepared. The Mannich product 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 quaternary ammonium
internal
salt was oleylamidopropyl dimethylammonium from Example 1; the propoxylated
alcohol
was a blend of commercially available C16-C18 propoxylated alcohols; and the
succinimide detergent was a 950 number average molecular weight polyisobutenyl
mono-
succinimide derived from tetraethylene pentaamine (TEPA).
[00086] Table 2
Inventive 1 Inventive 2
Ingredients
ppmw
ppmw
Mannich Detergent
82.4 82.4
Quaternary Ammonium
Internal Salt 2.0 2.0
Propoxylated alcohol
33.1 41.2
Mono-Succinimide 3.1
3.1
Propoxylated alcohol to
Mannich detergent weight 0.40:1 0.50:1
ratio
Mannich detergent to
Quaternary ammonium salt
41.2:1 41.2:1
weight ratio
* The additive package also contained other non-detergent ingredients, such as
demulsifier and solvent.
[00087] The additive packages of Table 2 were blended into Base Fuel A at the
treat
rates set forth in Table 3 below. The fuel was then evaluated for intake valve
deposits and
CA 3211252 2023-09-06
improvements from the base fuel without the additive determined pursuant to
ASTM
D6201.
[00088] Table 3
Base Fuel Inventive 1 Inventive 2
IVD testing
ASTM D6201,
1263.1 62.7 53.9
IVD, mg
improvement from
Base Fuel A IVD, 95.0 95.7
[00089] As shown in Table 3 above, the inventive samples exhibited good IVD
results.
[00090] EXAMPLE 3
[00091] The fuel additives of Example 2 where further evaluated in an additive
package
of Table 4 below. The additives were the same as Example 2 except Inventive 4
included
a bis-succinimide instead of a mono-succinimide as noted in Table 4.
[00092] Table 4
Comparative 1 Inventive 3 Inventive 4
Ingredients
PPmw PPmw PPmw
Mannich Detergent
164.1 164 164
Quaternary Ammonium
Internal Salt 2.3 2.3
Propoxylated alcohol
49.2 49.2 49.2
Mono-Succinimide 5.6
5.6
Bis-Succinimide
7.1
Propoxylated alcohol to
Mannich detergent weight 0.30/1 0.30/1 0.30/1
ratio
Mannich detergent to
Quaternary ammonium 71.3: 1
71.3: 1
salt weight ratio
* The additive package also contained other non-detergent ingredients, such as
demulsifier and
solvent.
[00093] A series of tests were run to evaluate the impact that the additive
packages have
on fuel inject deposits in a gasoline direct injection engine (GDI). All tests
were run with a
31
CA 3211252 2023-09-06
consistent Base Fuel B during a Dirty-up (DU), Clean-up (CU) and/or Keep Clean
(KC)
phases of the respective test. The additive packages of Table 4 above were
tested to
evaluate the ability of each fuel additive to improve injector performance by
reducing
injector deposits in the GDI engine.
[00094] Each base fuel 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.
[00095] In order to accelerate the DU phase of the Base Fuel, a combination of
di-tert-
butyl disulfide (DTBDS 406.1ppmw) and tert-butyl hydrogen peroxide (TBHP,
286ppmw)
were added to the base fuel and the DU was accelerated to provide the fouling
in the range
of 5-12%. Percent of fouling is calculated as:
Injector pulse width¨injec pulse width at start of testing * 100%
Percent of fouling: =
injector pulse at start of testing
[00096] GDI 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 4 were blended into the Base Fuel B that was used for DU.
The test
procedure consists 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 at the treat rates set forth
in Table 5 below,
which demonstrated a clean-up (CU) of over 100% within 48 hours. CU is
calculated as in
the following equation:
32
CA 3211252 2023-09-06
,
= Injector pulse
width at end of DU ¨ injector pulse width at end of testing
CU _____________
Injector pulse width at end of DU ¨ injector pulse width at starting of
testing
* 100%
[00097] Table 5
Comparative 1 Inventive 3 Inventive 4
Mannich, ppmw 164.1 164.0 164.0
Quaternary
ammonium salt, 0
2.3 2.3
PPmw
GDI CU by RIFT
79.9 100.09 101.9
method, %
[00098] As shown in Table 5 above, the inventive examples exhibited improved
injector
clean-up relative to the comparative example. Furthermore, GDI keep-clean (KC)
was
demonstrated by using the additive package of Table 1 in the base fuel at a
certain treat
rate on a GM LHU engine. The duration of the KC phase was 66 hours. In the KC
phase,
it can be seen that the additive package of Inventive 1 prevented deposits
from being
formed in the fuel as shown in Figure 1. Once the additive is added, the LTFT
decreased
from about 0.78% to about -3.14% as shown in Figure 2.
[00099] GDI CU deposit tests in Table 6 were carried out on a
2008 Pontiac Solstice
vehicle. The additive packages were blended into Base Fuel C. The DU procedure
was
running by RTFT method described previously between 2000-3000 miles to achieve
delta
LTFT (A = end of DU- beginning of DU) of about 6.0% or above. At the end of
DU, the
fuel was changed to an additized formulation that is designed to have a clean-
up effect
[000100] Table 6
Inventive 5 Comparative 2
Comparative 3
Composition
PPmw PPmw PPmw
Mannich
79.6 0 79.6
Detergent
Quaternary
Ammonium 0
Internal Salt 2.9 2.9
Propoxylated
alcohol 23.9 23.9 23.9
33
CA 3211252 2023-09-06
,
LTFT in the
beginning of -3.1 -3.9 -5.5
DU, %
LTFT at the end
4.7 6.3 5.5
of DU, %
LTFT at the end
0.8 7.8 3.9
of CU, %
GDI CU, % 50.0 -14.7 14.5
[000101] With combination of Mannich and Quaternary ammonium salt, the CU% is
50% while Mannich alone provided 14.5% GDI CU and quaternary ammonium salt -
14.7% (continuing DU) as shown in FIG. 3.
¨(LTFT at end of CU ¨ LTFT at end of DU)x100%
CU% = _______________________________________
(LTFT at end of DU ¨ LTFT in the begining of DU)
[000102] 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
[000103] 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.
34
CA 3211252 2023-09-06
,
[000104] 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.
.. [000105] 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.
[000106] 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.
[000107] 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.
35
CA 3211252 2023-09-06
