Note: Descriptions are shown in the official language in which they were submitted.
1
USE OF QUATERNIZED ALKYLAMINES AS ADDITIVES IN FUELS AND LUBRICANTS
The present invention relates to the use of quaternized alkylamine nitrogen
compounds as a
fuel additive and lubricant additive, such as, more particularly, as a
detergent additive; for
reduction or prevention of deposits in the injection systems of direct
injection diesel engines,
especially in common rail injection systems, for reduction of the fuel
consumption of direct
injection diesel engines, especially of diesel engines with common rail
injection systems, and
for minimization of power loss in direct injection diesel engines, especially
in diesel engines
with common rail injection systems; and as an additive for gasoline fuels,
especially for
operation of DISI engines.
State of the art:
In direct injection diesel engines, the fuel is injected and distributed
ultrafinely (nebulized) by
a multihole injection nozzle which reaches directly into the combustion
chamber of the engine,
instead of being introduced into a prechamber or swirl chamber as in the case
of the
conventional (chamber) diesel engine. The advantage of the direct injection
diesel engines
lies in their high performance for diesel engines and nevertheless low fuel
consumption.
Moreover, these engines achieve a very high torque even at low speeds.
At present, essentially three methods are being used for injection of the fuel
directly into the
combustion chamber of the diesel engine: the conventional distributor
injection pump, the
pump-nozzle system (unit-injector system or unit-pump system), and the common
rail system.
In the common rail system, the diesel fuel is conveyed by a pump with
pressures up to 2000
bar into a high-pressure line, the common rail. Proceeding from the common
rail, branch lines
run to the different injectors which inject the fuel directly into the
combustion chamber. The
full pressure is always applied to the common rail, which enables multiple
injection or a
specific injection form. In the other injection systems, in contrast, only
smaller variation in the
injection is possible. The injection in the common rail is divided essentially
into three groups:
(1.) pre-injection, by which essentially softer combustion is achieved, such
that harsh
combustion noises ("nailing") are reduced and the engine seems to run quietly;
(2.) main
injection, which is responsible especially for a good torque profile; and (3.)
post-injection,
which especially ensures a low NO, value. In this post-injection, the fuel is
generally not
Date Recue/Date Received 2020-12-09
2
combusted, but instead vaporized by residual heat in the cylinder. The exhaust
gas/fuel
mixture formed is transported to the exhaust gas system, where the fuel, in
the presence of
suitable catalysts, acts as a reducing agent for the nitrogen oxides NOR.
The variable, cylinder-individual injection in the common rail injection
system can positively
influence the pollutant emission of the engine, for example the emission of
nitrogen oxides
(NOR), carbon monoxide (CO) and especially of particulates (soot). This makes
it possible, for
example, for engines equipped with common rail injection systems to meet the
Euro 4
standard theoretically even without additional particulate filters.
In modern common rail diesel engines, under particular conditions, for example
when
biodiesel-containing fuels or fuels with metal impurities such as zinc
compounds, copper
compounds, lead compounds and other metal compounds are used, deposits can
form on
the injector orifices, which adversely affect the injection performance of the
fuel and hence
impair the performance of the engine, i.e. especially reduce the power, but in
some cases
also worsen the combustion. The formation of deposits is enhanced further by
further
developments in the injector construction, especially by the change in the
geometry of the
nozzles (narrower, conical orifices with rounded outlet). For lasting optimal
functioning of
engine and injectors, such deposits in the nozzle orifices must be prevented
or reduced by
suitable fuel additives.
In the injection systems of modern diesel engines, deposits cause significant
performance
problems. It is common knowledge that such deposits in the spray channels can
lead to a
decrease in the fuel flow and hence to power loss. Deposits at the injector
tip, in contrast,
impair the optimal formation of fuel spray mist and, as a result, cause
worsened combustion
and associated higher emissions and increased fuel consumption. In contrast to
these
conventional "external" deposition phenomena, "internal" deposits (referred to
collectively as
internal diesel injector deposits (IDID)) in particular parts of the
injectors, such as at the nozzle
needle, at the control piston, at the valve piston, at the valve seat, in the
control unit and in
the guides of these components, also increasingly cause performance problems.
Conventional additives exhibit inadequate action against these IDIDs.
US 4,248,719 describes quaternized ammonium salts which are prepared by
reacting an
alkenylsuccinimide with a monocarboxylic ester and find use as dispersants in
lubricant oils
Date Recue/Date Received 2020-12-09
3
for prevention of sludge formation. More particularly, for example, the
reaction of
polyisobutylsuccinic anhydride (PI BSA) with N,N-dimethylaminopropylamine
(DMAPA) and
quaternization with methyl salicylate is described. However, use in fuels,
more particularly
diesel fuels, is not proposed therein. The use of PIBSA with low bismaleation
levels of < 20%
is not described therein.
US 4,171,959 describes quaternized ammonium salts of hydrocarbyl-substituted
succinimides, which are suitable as detergent additives for gasoline fuel
compositions.
Quaternization is preferably accomplished using alkyl halides. Also mentioned
are organic
C2-C8-hydrocarbyl carboxylates and sulfonates. Consequently, the quaternized
ammonium
salts provided according to the teaching therein have, as a counterion, either
a halide or a C2-
C8-hydrocarbyl carboxylate or a C2-C8-hydrocarbyl sulfonate group. The use of
PIBSA with
low bismaleation levels of < 20% is likewise not described therein.
EP-A-2 033 945 discloses cold flow improvers which are prepared by
quaternizing specific
tertiary monoamines bearing at least one C8-C40-alkyl radical with a C1-C4-
alkyl ester of
specific carboxylic acids. Examples of such carboxylic esters are dimethyl
oxalate, dimethyl
maleate, dimethyl phthalate and dimethyl fumarate. Uses other than that for
improvement of
the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945.
WO 2006/135881 describes quaternized ammonium salts prepared by condensation
of a
hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-
containing
compound with a tertiary amino group, and subsequent quaternization by means
of
hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid such
as, more
particularly, acetic acid. Further quaternizing agents claimed in WO
2006/135881 are dialkyl
sulfates, benzyl halides and hydrocarbyl-substituted carbonates, and dimethyl
sulfate, benzyl
chloride and dimethyl carbonate have been studied experimentally.
The quaternizing agents used with preference in WO 2006/135881, however, have
serious
disadvantages such as: toxicity or carcinogenicity (for example in the case of
dimethyl sulfate
and benzyl halides), no residue-free combustion (for example in the case of
dimethyl sulfate
and alkyl halides), and inadequate reactivity which leads to incomplete
quaternization or
uneconomic reaction conditions (long reaction times, high reaction
temperatures, excess of
quaternizing agent; for example in the case of dimethyl carbonate).
Date Recue/Date Received 2020-12-09
4
EP-A-2 033 945 describes the preparation of halogen- and sulfur-free
quaternary ammonium
salts of organic carboxylic acids (for example oxalic acid, phthalic acid,
salicylic acid, malonic
acid and maleic acid, and the alkyl esters thereof) and the use thereof for
improvement of the
CFPP value of diesel fuels.
Quaternary ammonium salts of alpha-hydroxycarboxylic acids are proposed in EP-
A-1 254
889 as cleaning agents for electronic components.
In addition, Japanese patent application, application number 61-012197,
describes the use
of quaternary ammonium salts of organic carboxylic acids as surfactants or raw
materials for
medicaments or cosmetics.
It was therefore an object of the present invention to provide further fuel
additives which
prevent deposits in the injector tip and internal injector deposits in the
course of operation of
common rail diesel engines.
Brief description of the invention:
It has now been found that, surprisingly, the above object is achieved by
providing
quaternized hydrocarbylamine compounds and fuel and lubricant compositions
additized
therewith.
Surprisingly, the inventive additives, as illustrated more particularly by the
appended use
examples, are surprisingly effective in common rail diesel engines and are
notable for their
particular suitability as an additive for reducing power loss resulting from
external deposits
and cold start problems resulting from internal deposits.
Description of figures:
Figure 1 shows a measurement of the time-dependent (h) change in the exhaust
gas
temperatures of the cylinders in the case of use of a fuel without additive;
large deviations in
the temperature are caused by internal injector deposits.
Figure 2 shows the time-dependent (h) change in the exhaust gas temperatures
in the same
cylinders as in figure 1, but now after treatment with the inventive additive
from preparation
example 3, dosage 394 mg/kg.
Date Recue/Date Received 2020-12-09
5
Figure 3 shows the profile of a one-hour engine test cycle to CEC F-098-08.
Detailed description of the invention:
Al) Specific embodiments
The present invention relates especially to the following specific
embodiments:
1. A fuel composition or lubricant composition comprising, in a majority of
a customary
fuel or lubricant, a proportion, especially an effective amount, of at least
one reaction
product comprising a quaternized nitrogen compound, or a fraction thereof
which
comprises a quaternized nitrogen compound and is obtained from the reaction
product
by purification, said reaction product being obtainable by
reacting a quaternizable alkylamine comprising at least one quaternizable
tertiary
amino group with a quaternizing agent which converts the at least one tertiary
amino
group to a quaternary ammonium group,
the quaternizing agent being the alkyl ester of a cycloaromatic or
cycloaliphatic mono-
or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an
aliphatic
polycarboxylic acid, especially dicarboxylic acid, a hydrocarbyl epoxide,
optionally in
combination with a free acid, or a dialkyl carbonate such as di-C1-C4-
carbonate,
especially dimethyl carbonate.
2. The fuel composition or lubricant composition according to embodiment
1, wherein the
alkylamine comprises at least one compound of the following general formula 3
RaRbIR,N (3)
in which
at least one of the Ra, Rb and IR, radicals, for example one or two, is a
straight-chain or
branched, saturated or unsaturated C8-C40-hydrocarbyl radical (especially
straight-
chain or branched C8-C40-alkyl) and the remaining radicals are identical or
different,
straight-chain or branched, saturated or unsaturated C1-C6-hydrocarbyl
radicals
(especially Ci-C6-alkyl); or
2a. The fuel composition or lubricant composition according to embodiment
1, wherein the
alkylamine comprises at least one compound of the following general formula 3
Date Recue/Date Received 2020-12-09
6
RaRbR,N (3)
in which all Ra, Rb and IR, radicals are identical or different, straight-
chain or branched,
saturated or unsaturated C8-C40-hydrocarbyl radicals, especially straight-
chain or
branched C8-C40-alkyl radicals.
3. The fuel composition or lubricant composition according to any of the
preceding
embodiments, wherein the quaternizing agent is a compound of the general
formula 1
R10C(0)R2 (1)
in which
R1 is a low molecular weight hydrocarbyl radical such as alkyl or
alkenyl radical,
especially a lower alkyl radical such as, more particularly, methyl or ethyl,
and
R2 is an optionally substituted monocyclic hydrocarbyl radical,
especially an aryl or
cycloalkyl or cycloalkenyl radical, especially aryl such as phenyl, where the
substituent
is selected from OH, NH2, NO2, C(0)0R3, and R10C(0)-, in which R1 is as
defined
above and R3 is H or R1, where the substituent is especially OH. More
particularly, the
quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate
or methyl
salicylate.
4. The fuel composition according to either of embodiments 1 and 2, wherein
the
quaternizing agent is a compound of the general formula 2
R10C(0)-A-C(0)0Ria (2)
in which
R1 and Ria are each independently a low molecular weight hydrocarbyl radical
such as
an alkyl or alkenyl radical, especially a lower alkyl radical, and
A is an optionally mono- or polysubstituted hydrocarbylene (such as, more
particularly,
an optionally mono- or polysubstituted C1-C7-alkylene or C2-C7-alkenylene);
where
suitable substituents, for example, are selected from OH, NH2, NO2, or
C(0)0R3,
especially OH and C(0)0R3, where R3 is as defined above.
5. The fuel composition or lubricant composition according to either of
embodiments 1
and 2, wherein the quaternizing agent comprises an epoxide of the general
formula 4
Date Recue/Date Received 2020-12-09
7
R. R
d
(4)
Rd Rd
where
the Rd radicals present therein are the same or different and are each H or a
hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic
radical
having at least 1 to 10 carbon atoms and the free acid of the quaternizing
agent is a
free protic acid, especially a C1_12-mono-, -di- or -oligocarboxylic acid.
6. The fuel composition or lubricant composition according to any of the
preceding
embodiments, wherein the quaternizable tertiary amine is a compound of the
formula
3 in which at least two of the Ra, Rb and IR, radicals are the same or
different and are
each a straight-chain or branched Cio-C20-alkyl radical and the other radical
is Ci-C4-
alkyl.
7. The fuel composition or lubricant composition according to any of the
preceding
embodiments, wherein the quaternizing agent is selected from lower alkylene
oxides
in combination with a monocarboxylic acid, alkyl salicylates, dialkyl
phthalates and
dialkyl oxalates.
8. The fuel composition or lubricant composition according to any of the
preceding
embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels, and
alkanol-
containing gasoline fuels, such as bioethanol-containing fuels, especially
diesel fuels.
9. A quaternized nitrogen compound as defined in any of embodiments 1 to 7.
10. A process for preparing a quaternized nitrogen compound according to
embodiment 9,
comprising the reaction of a quaternizable alkylamine comprising at least one
quaternizable tertiary amino group with a quaternizing agent which converts
the at least
one tertiary amino group to a quaternary ammonium group,
the quaternizing agent being the alkyl ester of a cycloaromatic or
cycloaliphatic mono-
or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an
aliphatic
Date Recue/Date Received 2020-12-09
8
polycarboxylic acid, especially dicarboxylic acid, or a hydrocarbyl epoxide in
combination with an acid.
11.
The use of a quaternized nitrogen compound according to embodiment 9 or
prepared
according to embodiment 10 as a fuel additive or lubricant additive.
12. The use according to embodiment 11 as an additive for reducing the fuel
consumption
of direct injection diesel engines, especially of diesel engines with common
rail injection
systems, and/or for minimizing power loss in direct injection diesel engines,
especially
in diesel engines with common rail injection systems (for example determined
in a
DW10 test based on CEC F-098-08, as described in detail in the experimental
below).
13. The use according to embodiment 11 as a gasoline fuel additive for
reducing the level
of deposits in the intake system of a gasoline engine, such as, more
particularly, DISI
and PFI (port fuel injector) engines.
14. The use according to embodiment 10 as a diesel fuel additive for reducing
and/or
preventing deposits in the injection systems, for example determined in a XUD
9 test
to CEC-F-23-1-01, such as, more particularly, the internal diesel injector
deposits
(IDIDs), and/or valve sticking in direct injection diesel engines, especially
in common
rail injection systems (for example determined by an IDID test procedure as
described
in detail in the experimental below).
15. An additive concentrate comprising, in combination with further diesel
fuel additives or
gasoline fuel additives or lubricant additives, at least one quaternized
nitrogen
compound as defined in embodiment 9 or prepared according to embodiment 10.
Test methods suitable for examination of each of the above-designated
applications are
known to those skilled in the art, or are described in the experimental which
follows, to which
explicit and general reference is hereby made.
A2) General definitions
In the absence of statements to the contrary, the following general
definitions apply:
Date Recue/Date Received 2020-12-09
9
"Hydrocarbyl" can be interpreted widely and comprises both long-chain and
short-chain,
straight-chain and branched hydrocarbyl radicals having 1 to 50 carbon atoms,
which may
optionally additionally comprise heteroatoms, for example 0, N, NH, S, in the
chain thereof.
A specific group of hydrocarbyl radicals comprises both long-chain and short-
chain, straight-
chain or branched alkyl radicals having 1 to 50 carbon atoms.
"Long-chain" hydrocarbyl radicals are straight-chain or branched hydrocarbyl
radicals and
have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which may
optionally additionally
comprise heteroatoms, for example 0, N, NH, S, in the chain thereof. In
addition, the radicals
may be mono- or polyunsaturated and have one or more noncumulated, for example
1 to 5,
such as 1, 2 or 3, C-C double bonds or C-C triple bonds, especially 1, 2 or 3
double bonds.
They may be of natural or synthetic origin. They may also have a number-
average molecular
weight (Me) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or
350 to 5000, for
example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. In that case,
they are more
particularly formed essentially from C2_6, especially C2_4, monomer units such
as ethylene,
propylene, n- or isobutylene or mixtures thereof, where the different monomers
may be
copolymerized in random distribution or as blocks. Such long-chain hydrocarbyl
radicals are
also referred to as polyalkylene radicals or poly-C2_6- or poly-C2_4-alkylene
radicals. Suitable
long-chain hydrocarbyl radicals and the preparation thereof are also
described, for example,
in WO 2006/135881 and the literature cited therein. A specific group of long-
chain hydrocarbyl
radicals comprises straight-chain or branched alkyl radicals ("long-chain"
alkyl radicals)
having 8 to 50, for example 8 to 40 or 8 to 30 or 10 to 20, carbon atoms.
"Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" is especially
straight-chain
or branched alkyl or alkenyl, optionally interrupted by one or more, for
example 2, 3 or 4,
heteroatom groups such as -0- or ¨NH-, or optionally mono- or polysubstituted,
for example
di-, tri- or tetrasubstituted.
"Hydrocarbylene" represents straight-chain or singly or multiply branched
bridging groups
having 1 to 10 carbon atoms, optionally interrupted by one or more, for
example 2, 3 or 4,
heteroatom groups such as -0- or ¨NH-, or optionally mono- or polysubstituted,
for example
di-, tri- or tetrasubstituted.
Date Recue/Date Received 2020-12-09
10
"Alkyl" or "lower alkyl" represents especially saturated, straight-chain or
branched
hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms,
for example methyl,
ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-
dimethylethyl, n-
pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-
ethylpropyl, n-
hexyl, 1, 1-dimethyl propyl, 1,2-di methyl propyl , 1-
methylpentyl, 2-methyl pentyl, 3-
methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-
dimethylbutyl, 2,2-
dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-
ethylbutyl, 1,1,2-
trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-
methylpropyl; and
also n-heptyl, and the singly or multiply branched analogs thereof.
"Long-chain alkyl" especially represents saturated, straight-chain or branched
hydrocarbyl
radicals having 8 to 50, for example 8 to 40 or 8 to 30 or 10 to 20, carbon
atoms, such as
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl,
octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl,
pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers, especially
singly or multiply
branched isomers and higher homologs thereof.
"Alkenyl" represents mono- or polyunsaturated, especially monounsaturated,
straight-chain
or branched hydrocarbon radicals having 2 to 4, 2 to 6 or 2 to 7 carbon atoms
and a double
bond in any position, for example C2-C6-alkenyl such as ethenyl, 1-propenyl, 2-
propenyl,
1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-
methyl-1-propenyl,
.. 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-
pentenyl, 4-pentenyl,
1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-
butenyl, 2-methyl-2-
butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-
3-butenyl,
1, 1-di methy1-2-propenyl, 1,2-di methy1-1-propenyl,
1,2-di methy1-2-propenyl, 1-ethyl-1-
propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-
hexenyl,
1-methyl-1-pentenyl, 2-m ethyl-1-pentenyl , 3-methyl-1-
pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-m ethyl-2-pentenyl ,
3-methyl-2-pentenyl, 4-methyl-2-pentenyl,
1-methyl-3-pentenyl, 2-m ethyl-3-pentenyl ,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl,
1-methyl-4-pentenyl, 2-m ethyl-4-pentenyl ,
3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1, 1-di methy1-2-butenyl , 1,1-di methy1-3-butenyl , 1,2-di methy1-1-butenyl ,
1,2-di methyl-2-
butenyl, 1,2-dimethy1-3-butenyl, 1,3-dimethy1-1-butenyl, 1,3-dimethy1-2-
butenyl, 1,3-dimethy1-
3-butenyl, 2,2-dimethy1-3-butenyl,
2,3-dimethy1-1-butenyl, 2,3-dimethy1-2-butenyl,
2,3-dimethy1-3-butenyl, 3,3-dimethy1-1-butenyl, 3,3-dimethy1-2-butenyl, 1-
ethyl-1-butenyl,
Date Recue/Date Received 2020-12-09
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1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-
ethyl-3-butenyl,
1,1,2-trimethy1-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-
propenyl and
1-ethyl-2-methyl-2-propenyl.
"Alkylene" represents straight-chain or mono- or polybranched hydrocarbon
bridging groups
having 1 to 10 carbon atoms, for example C1-C7-alkylene groups selected from -
CH2-, -(CH2)2-,
-(CH2)3-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -(CH2)4-, -(CH2)2-CH(CH3)-, -CH2-
CH(CH3)-CH2-,
(CH2)4-, -(CH2)6-, -(CH2)6, -(CH2)7-, -CH(CH3)-CH2-CH2-CH(CH3)- or
-CH(CH3)-CH2-CH2-CH2-CH(CH3)- or C1-C4-alkylene groups selected from -CH2-, -
(CH2)2-,
-(CH2)3-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -(CH2)4-, -(CH2)2-CH(CH3)-, -CH2-
CH(CH3)-CH2-.
"Alkenylene" represents the mono- or polyunsaturated, especially
monounsaturated, analogs
of the above alkylene groups having 2 to 10 carbon atoms, especially C2-C7-
alkenylenes or
C2-C4-alkenylene, such as -CH=CH-, -CH=CH-CH2-, - CH2-CH=CH-,
-CH=CH-CH2-CH2-, -CH2-CH=CH-CH2-, -CH2-CH2-CH=CH-, -CH(CH3)-CH=CH-,
-CH2-C(CH3)=CH-.
"Cycloalkyl" represents carbocyclic radicals having 3 to 20 carbon atoms, for
example C3-C12-
cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl,
cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to
cyclopentyl,
cyclohexyl, cycloheptyl, and also cyclopropylmethyl, cyclopropylethyl,
cyclobutylmethyl,
cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C3-
C7-cycloalkyl
such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclopropylmethyl,
cyclopropyl ethyl, cyclobutylm ethyl, cyclopentylethyl, cyclohexyl methyl,
where the bond to the
rest of the molecule may be via any suitable carbon atom.
"Aryl" represents mono- or polycyclic, preferably mono- or bicyclic,
optionally substituted
aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for
example phenyl,
biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl,
indenyl and
phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5 or 6
identical or different
substituents.
"Substituents" for radicals specified herein are especially, unless stated
otherwise, selected
from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO2, alkyl, or
alkenyl groups.
Date Recue/Date Received 2020-12-09
12
"Mn" represents the number-average molecular weight and is determined in a
conventional
manner; more particularly, such statements relate to Mn values determined by
gel permeation
chromatography.
A3) Tertiary amines of the formula (3)
Tertiary amines of the formula (3) are compounds known per se, as described,
for example,
in EP-A-2 033 945.
The tertiary amine reactant (3) preferably bears a segment of the formula NR,
Rb where one
of the radicals has an alkyl group having 8 to 40 carbon atoms and the other
an alkyl group
having up to 40 and more preferably 8 to 40 carbon atoms. The IR, radical is
especially a
short-chain C1-C6-alkyl radical, such as a methyl, ethyl or propyl group. Ra
and Rb may be
straight-chain or branched, and/or may be the same or different. For example,
IR, and Rb may
be a straight-chain C12-C24-alkyl group. Alternatively, only one of the two
radicals may be
long-chain (for example having having 8 to 40 carbon atoms), and the other may
be a methyl,
ethyl or propyl group.
Appropriately, the NRaRb segment is derived from a secondary amine, such as
dioctadecylamine, dicocoamine, hydrogenated ditallowamine and
methylbehenylamine.
Amine mixtures as obtainable from natural materials are likewise suitable. One
example is a
secondary hydrogenated tallowamine where the alkyl groups are derived from
hydrogenated
tallow fat, and contain about 4% by weight of C14, 31% by weight of C16 and
59% by weight
of C18-alkyl groups. Corresponding tertiary amines of the formula (3) are
sold, for example,
by Akzo Nobel under the Armeene M2HT or Armeene M2C name.
The tertiary amine reactant (3) may also take such a form that the Ra, Rb and
IR, radicals have
identical or different long-chain alkyl radicals, especially straight-chain or
branched alkyl
groups having 8 to 40 carbon atoms.
Further nonlimiting examples of suitable amines are:
N,N-dimethyl-N-(2-ethylhexyl)amine, N,N-dimethyl-N-(2-propylheptyl)amine,
dodecyl-
dimethylamine, hexadecyldimethylamine, oleyldimethylamine,
cocoyldimethylamine,
dicocoylmethylamine, tallowdimethylamine, ditallowmethylamine,
tridodecylamine,
Date Recue/Date Received 2020-12-09
13
trihexadecylamine, trioctadecylamine, soyadimethylamine, tris(2-
ethylhexyl)amine, and
Alamine 336 (tri-n-octylamine).
A4) Quaternizing agents:
Useful quaternizing agents in principle include all compounds suitable as
such. The
quaternizing agent is especially selected from alkylene oxides, optionally in
combination with
acid; aliphatic or aromatic carboxylic esters such as, more particularly,
dialkyl carboxylates;
alkanoates; cyclic nonaromatic or aromatic carboxylic esters; alkyl sulfates;
alkyl halides;
alkylaryl halides; dialkyl carbonates; and mixtures thereof.
Suitable examples are alkyl esters, derived from carboxylic acids, whose pK,
is less than 3.5.
Examples are especially alkyl esters derived from oxalic acid, phthalic acid,
salicylic acid,
maleic acid, malonic acid and citric acid.
In a particular embodiment, however, the at least one quaternizable tertiary
nitrogen atom is
quaternized with at least one quaternizing agent selected from
a) compounds of the general formula 1
R10C(0)R2 (1)
in which
R1 is a lower alkyl radical and
R2 is an optionally substituted monocyclic aryl or cycloalkyl radical,
where the substituent
is selected from OH, NH2, NO2, C(0)0R3; Ria0C(0)- in which Ria is as defined
above for R1,
and R3 is H or Ri;
or
b) compounds of the general formula 2
R10C(0)-A-C(0)0Ria (2)
in which
R1 and Ria are each independently a lower alkyl radical and
A is an optionally mono- or polysubstituted hydrocarbylene (such as,
more particularly, an
optionally mono- or polysubstituted C1-C7-alkylene or C2-C7-alkenylene); where
suitable
Date Recue/Date Received 2020-12-09
14
substituents, for example, are selected from OH, NH2, NO2, or C(0)0R3,
especially OH and
C(0)0R3, where R3 is as defined above.
Particularly suitable compounds of the formula 1 are those in which
R1 is a C1-, C2- or C3-alkyl radical and
R2 is a substituted phenyl radical, where the substituent is HO- or an
ester radical of the
formula Ria0C(0)- which is in the para, meta or especially ortho position to
the R10C(0)-
radical on the aromatic ring.
Especially suitable quaternizing agents are the lower alkyl esters of
salicylic acid, such as
methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or
tert-butyl salicylate.
Abovementioned esters are typically used in the presence of acids, especially
in the presence
of free protic acids such as, in particular, with C1_12-monocarboxylic acids
such as formic acid,
acetic acid or propionic acid, or C2_12-dicarboxylic acids such as oxalic acid
or adipic acid; or
else in the presence of sulfonic acids such as benzenesulfonic acid or
toluenesulfonic acid,
or aqueous mineral acids such as sulfuric acid or hydrochloric acid.
c) In a further particular embodiment, the at least one quaternizable tertiary
nitrogen atom is
quaternized with at least one quaternizing agent selected from epoxides,
especially
hydrocarbyl epoxides.
R. R
d
d'111-y <4.
(4)
Rd Rd
where the Rd radicals present therein are the same or different and are each H
or a
hydrocarbyl radical, where the hydrocarbyl radical has at least 1 to 10 carbon
atoms. These
are especially aliphatic or aromatic radicals, for example linear or branched
C1_10-alkyl
radicals, or aromatic radicals such as phenyl or C1_4-alkylphenyl.
Examples of suitable hydrocarbyl epoxides include aliphatic and aromatic
alkylene oxides
such as, more particularly, C2_12-alkylene oxides such as ethylene oxide,
propylene oxide,
1 ,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene
oxide),
1 ,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1
,2-butene oxide,
Date Recue/Date Received 2020-12-09
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1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene
oxide, 2-ethyl-
1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene
oxide or
4-methyl-1,2-pentene oxide; and aromatic-substituted ethylene oxides such as
optionally
substituted styrene oxide, especially styrene oxide or 4-methylstyrene oxide.
In the case of use of epoxides as quaternizing agents, these are used in the
presence or in
the absence of free acids, especially in the presence or absence of free
protic acids, such as,
in particular, with C1_12-monocarboxylic acids such as formic acid, acetic
acid or propionic
acid, or C212-dicarboxylic acids such as oxalic acid or adipic acid; or else
in the presence or
absence of sulfonic acids such as benzenesulfonic acid or toluenesulfonic
acid, or aqueous
mineral acids such as sulfuric acid or hydrochloric acid. The quaternization
product thus
prepared is thus either "acid-containing" or "acid-free" in the context of the
present invention.
A5) Preparation of inventive additives:
a) Quaternization
The quaternization is performed in a manner known per se.
(1) To perform the quaternization, the tertiary amine is admixed with at least
one compound
of the above formula 1 or 2, especially in the stoichiometric amounts required
to achieve the
desired quaternization. It is possible to use, for example, 0.1 to 5.0, 0.2 to
3.0 or 0.5 to 2.5
equivalents of quaternizing agent per equivalent of quaternizable tertiary
nitrogen atom. More
particularly, however, about 1 to 2 equivalents of quaternizing agent are used
in relation to
the tertiary amine, in order to fully quaternize the tertiary amine group.
Typical working temperatures here are in the range from 50 to 180 C, for
example 90 to
160 C or 100 to 140 C. The reaction time may be in the region of a few minutes
or a few
hours, for example about 10 minutes up to about 24 hours. The reaction can be
effected at a
pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3 bar, but
especially at about
standard pressure.
If required, the reactants can be initially charged for the quaternization in
a suitable inert
organic aliphatic or aromatic solvent or a mixture thereof. Typical examples
are, for example,
Date Recue/Date Received 2020-12-09
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solvents of the Solvesso series, toluene or xylene, or ethylhexanol. The
quaternization can,
however, also be performed in the absence of a solvent.
To perform the quaternization, the addition of catalytically active amounts of
an acid may be
appropriate. Preference is given to aliphatic monocarboxylic acids, for
example
C1-C18-monocarboxylic acids such as, more particularly, lauric acid,
isononanoic acid or 3,3,5-
trimethylhexanoic acid or neodecanoic acid, but also aliphatic dicarboxylic
acids or polybasic
aliphatic carboxylic acids with a carbon atom number in the range specified
above. The
quaternization can also be performed in the presence of a Lewis acid. The
quaternization
can, however, also be performed in the absence of any acid.
(2) The quaternization with an epoxide of the formula (4) is likewise effected
in a manner
known per se. When the boiling temperature of one component of the reaction
mixture,
especially of the epoxide, at standard pressure is above the reaction
temperature, the reaction
is appropriately performed in an autoclave.
For example, in an autoclave, a solution of the tertiary amine is admixed with
the organic acid
(for example acetic acid) in the required stoichiometric amounts. It is
possible to use, for
example, 0.1 to 2.0, 0.2 to 1.5 or 0.5 to 1.25 equivalents of acid per
equivalent of quaternizable
tertiary nitrogen atom. More particularly, however, approximately equimolar
proportions of the
acid are used. This is followed by sufficient purging with N2, and
establishment of a suitable
initial pressure, and metered addition of the epoxide (e.g. propylene oxide)
in the
stoichiometric amounts required at a temperature between 20 C and 180 C. It is
possible to
use, for example, 0.1 to 4.0, 0.2 to 3 or 0.5 to 2 equivalents of epoxide per
equivalent of
quaternizable tertiary nitrogen atom. More particularly, however, about 1 to 2
equivalents of
epoxide are used in relation to the tertiary amine, in order to fully
quaternize the tertiary amine
group. This is followed by stirring over a suitably long period of a few
minutes up to about 24
hours, for example about 10 h, at a temperature between 20 C and 180 C (e.g.
50 C),
cooling, for example to about 20 to 50 C, purging with N2 and emptying of the
reactor.
The reaction can be effected at a pressure of about 0.1 to 20 bar, for example
1 to 10 or 1.5
to 5 bar. However, the reaction can also be effected at standard pressure. An
inert gas
atmosphere is particular appropriate, for example nitrogen.
Date Recue/Date Received 2020-12-09
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If required, the reactants can be initially charged for the quaternization in
a suitable inert
organic aliphatic or aromatic solvent or a mixture thereof. Typical examples
are, for example,
solvents of the Solvesso series, toluene or xylene, or 2-ethylhexanol. The
quaternization can,
however, also be performed in the absence of a solvent.
The quaternization can be performed in the presence of a protic solvent,
optionally also in
combination with an aliphatic or aromatic solvent. Suitable protic solvents
especially have a
dielectric constant (at 20 C) of greater than 7. The protic solvent may
comprise one or more
OH groups, and may also be water. Suitable solvents may also be alcohols,
glycols and glycol
ethers. More particularly, suitable protic solvents may be those specified in
WO 2010132259.
Especially suitable solvents are methanol, ethanol, n-propanol, isopropanol,
all isomers of
butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-
propylheptanol, and
also mixtures of different alcohols. The presence of a protic solvent can
positively influence
the conversion and the reaction rate of the quaternization.
b) Workup of the reaction mixture
The reaction end product thus formed can theoretically be purified further, or
the solvent can
be removed. Optionally, excess reagent, for example excess epoxide, can be
removed. This
can be accomplished, for example, by introducing nitrogen at standard pressure
or under
reduced pressure. In order to improve the further processibility of the
products, however, it is
also possible to add solvents after the reaction, for example solvents of the
Solvesso series,
2-ethylhexanol, or essentially aliphatic solvents. However, this is usually
not absolutely
necessary, and so the reaction product can be used without further
purification as an additive,
optionally after blending with further additive components (see below).
B) Further additive components
The fuel additized with the inventive quaternized additive is a gasoline fuel
or especially a
middle distillate fuel, in particular a diesel fuel.
The fuel may comprise further customary additives to improve efficacy and/or
suppress wear.
In the case of diesel fuels, these are primarily customary detergent
additives, carrier oils, cold
flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers,
dehazers, antifoams,
Date Recue/Date Received 2020-12-09
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cetane number improvers, combustion improvers, antioxidants or stabilizers,
antistats,
metallocenes, metal deactivators, dyes and/or solvents.
In the case of gasoline fuels, these are in particular lubricity improvers
(friction modifiers),
corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers,
antioxidants
or stabilizers, antistats, metallocenes, metal deactivators, dyes and/or
solvents.
Typical examples of suitable coadditives are listed in the following section:
B1) Detergent additives
The customary detergent additives are preferably amphiphilic substances which
possess at
least one hydrophobic hydrocarbon radical with a number-average molecular
weight (Me) of
85 to 20 000 and at least one polar moiety selected from:
(Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one
nitrogen atom
having basic properties;
(Db) nitro groups, optionally in combination with hydroxyl groups;
(Dc) hydroxyl groups in combination with mono- or polyamino groups, at least
one nitrogen
atom having basic properties;
(Dd) carboxyl groups or the alkali metal or alkaline earth metal salts
thereof;
(De) sulfonic acid groups or the alkali metal or alkaline earth metal salts
thereof;
(DO polyoxy-C2- to C4-alkylene moieties terminated by hydroxyl groups,
mono- or polyamino
groups, at least one nitrogen atom having basic properties, or by carbamate
groups;
.. (Dg) carboxylic ester groups;
(Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino
and/or
amido and/or imido groups; and/or
(Di) moieties obtained by Mannich reaction of substituted phenols with
aldehydes and
mono- or polyamines.
Date Recue/Date Received 2020-12-09
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The hydrophobic hydrocarbon radical in the above detergent additives, which
ensures the
adequate solubility in the fuel, has a number-average molecular weight (Me) of
85 to 20 000,
preferably of 113 to 10 000, more preferably of 300 to 5000, even more
preferably of 300 to
3000, even more especially preferably of 500 to 2500 and especially of 700 to
2500, in
particular of 800 to 1500. As typical hydrophobic hydrocarbon radicals,
especially in
conjunction with the polar, especially polypropenyl, polybutenyl and
polyisobutenyl radicals
with a number-average molecular weight Mn of preferably in each case 300 to
5000, more
preferably 300 to 3000, even more preferably 500 to 2500, even more especially
preferably
700 to 2500 and especially 800 to 1500 into consideration.
Examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Da) are preferably
polyalkenemono- or
polyalkenepolyamines based on polypropene or on high-reactivity (i.e. having
predominantly
terminal double bonds) or conventional (i.e. having predominantly internal
double bonds)
polybutene or polyisobutene having Mn = 300 to 5000, more preferably 500 to
2500 and
especially 700 to 2500. Such additives based on high-reactivity polyisobutene,
which can be
prepared from the polyisobutene which may comprise up to 20% by weight of n-
butene units
by hydroformylation and reductive amination with ammonia, monoamines or
polyamines such
as dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or
tetraethylenepentamine, are known especially from EP-A 244 616. When
polybutene or
polyisobutene having predominantly internal double bonds (usually in the 13
and y positions)
are used as starting materials in the preparation of the additives, a possible
preparative route
is by chlorination and subsequent amination or by oxidation of the double bond
with air or
ozone to give the carbonyl or carboxyl compound and subsequent amination under
reductive
(hydrogenating) conditions. The amines used here for the amination may be, for
example,
ammonia, monoamines or the abovementioned polyamines. Corresponding additives
based
on polypropene are described more particularly in WO-A 94/24231.
Further particular additives comprising monoamino groups (Da) are the
hydrogenation
products of the reaction products of polyisobutenes having an average degree
of
polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and oxygen,
as described more particularly in WO-A 97/03946.
Date Recue/Date Received 2020-12-09
20
Further particular additives comprising monoamino groups (Da) are the
compounds
obtainable from polyisobutene epoxides by reaction with amines and subsequent
dehydration
and reduction of the amino alcohols, as described more particularly in DE-A
196 20262.
Additives comprising nitro groups (Db), optionally in combination with
hydroxyl groups, are
preferably reaction products of polyisobutenes having an average degree of
polymerization
P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides
and oxygen, as
described more particularly in WO-A 96/03367 and in WO-A 96/03479. These
reaction
products are generally mixtures of pure nitropolyisobutenes (e.g. a,8-
dinitropolyisobutene)
and mixed hydroxynitropolyisobutenes (e.g. a-nitro-8-hydroxypolyisobutene).
Additives comprising hydroxyl groups in combination with mono- or polyamino
groups (Dc)
are especially reaction products of polyisobutene epoxides obtainable from
polyisobutene
having preferably predominantly terminal double bonds and Mn = 300 to 5000,
with ammonia
or mono- or polyamines, as described more particularly in EP-A 476 485.
Additives comprising carboxyl groups or their alkali metal or alkaline earth
metal salts (Dd)
are preferably copolymers of C2- to C40-olefins with maleic anhydride which
have a total molar
mass of 500 to 20 000 and some or all of whose carboxyl groups have been
converted to the
alkali metal or alkaline earth metal salts and any remainder of the carboxyl
groups has been
reacted with alcohols or amines. Such additives are disclosed more
particularly by EP-A 307
815. Such additives serve mainly to prevent valve seat wear and can, as
described in WO-A
87/01126, advantageously be used in combination with customary fuel detergents
such as
poly(iso)buteneamines or polyetheramines.
Additives comprising sulfonic acid groups or their alkali metal or alkaline
earth metal salts
(De) are preferably alkali metal or alkaline earth metal salts of an alkyl
sulfosuccinate, as
described more particularly in EP-A 639 632. Such additives serve mainly to
prevent valve
seat wear and can be used advantageously in combination with customary fuel
detergents
such as poly(iso)buteneamines or polyetheramines.
Additives comprising polyoxy-C2-C4-alkylene moieties (Df) are preferably
polyethers or
polyetheramines which are obtainable by reaction of C2- to Caralkanols, C6- to
Car
alkanediols, mono- or di-C2- to C30-alkylamines, Ci- to C30-alkylcyclohexanols
or Ci- to C30-
alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or
butylene oxide
Date Recue/Date Received 2020-12-09
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per hydroxyl group or amino group and, in the case of the polyetheramines, by
subsequent
reductive amination with ammonia, monoamines or polyamines. Such products are
described
more particularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877
416. In the
case of polyethers, such products also have carrier oil properties. Typical
examples thereof
are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also
polyisobutenol butoxylates and propoxylates, and also the corresponding
reaction products
with ammonia.
Additives comprising carboxylic ester groups (Dg) are preferably esters of
mono-, di- or
tricarboxylic acids with long-chain alkanols or polyols, especially those
having a minimum
viscosity of 2 mm2/s at 100 C, as described more particularly in DE-A 38 38
918. The mono-,
di- or tricarboxylic acids used may be aliphatic or aromatic acids, and
particularly suitable
ester alcohols or ester polyols are long-chain representatives having, for
example, 6 to 24
carbon atoms. Typical representatives of the esters are adipates, phthalates,
isophthalates,
terephthalates and trimellitates of isooctanol, of isononanol, of isodecanol
and of
isotridecanol. Such products also satisfy carrier oil properties.
Additives comprising moieties derived from succinic anhydride and having
hydroxyl and/or
amino and/or amido and/or especially imido groups (Dh) are preferably
corresponding
derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially
the
corresponding derivatives of polyisobutenylsuccinic anhydride which are
obtainable by
reacting conventional or high-reactivity polyisobutene having Mn = preferably
300 to 5000,
more preferably 300 to 3000, even more preferably 500 to 2500, even more
especially
preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a
thermal route
in an ene reaction or via the chlorinated polyisobutene. The moieties having
hydroxyl and/or
amino and/or amido and/or imido groups are, for example, carboxylic acid
groups, acid
amides of monoamines, acid amides of di- or polyamines which, in addition to
the amide
function, also have free amine groups, succinic acid derivatives having an
acid and an amide
function, carboximides with monoamines, carboximides with di- or polyamines
which, in
addition to the imide function, also have free amine groups, or diimides which
are formed by
the reaction of di- or polyamines with two succinic acid derivatives. In the
presence of imido
moieties D(h), the further detergent additive in the context of the present
invention is,
however, used only up to a maximum of 100% of the weight of compounds with
betaine
structure. Such fuel additives are common knowledge and are described, for
example, in
Date Recue/Date Received 2020-12-09
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documents (1) and (2). They are preferably the reaction products of alkyl- or
alkenyl-
substituted succinic acids or derivatives thereof with amines and more
preferably the reaction
products of polyisobutenyl-substituted succinic acids or derivatives thereof
with amines. Of
particular interest in this context are reaction products with aliphatic
polyamines
(polyalkyleneimines) such as especially ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine
and
hexaethyleneheptamine, which have an imide structure.
Additives comprising moieties (Di) obtained by Mannich reaction of substituted
phenols with
aldehydes and mono- or polyamines are preferably reaction products of
polyisobutene-
substituted phenols with formaldehyde and mono- or polyamines such as
ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine
or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols may originate
from
conventional or high-reactivity polyisobutene having Mn = 300 to 5000. Such
"polyisobutene
Mannich bases" are described more particularly in EP-A 831 141.
One or more of the detergent additives mentioned can be added to the fuel in
such an amount
that the dosage of these detergent additives is preferably 25 to 2500 ppm by
weight,
especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight.
B2) Carrier oils
Carrier oils additionally used may be of mineral or synthetic nature. Suitable
mineral carrier
oils are the fractions obtained in crude oil processing, such as brightstock
or base oils having
viscosities, for example, from the SN 500 - 2000 class; but also aromatic
hydrocarbons,
paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction
which is obtained in
the refining of mineral oil and is known as "hydrocrack oil" (vacuum
distillate cut having a
boiling range of from about 360 to 500 C, obtainable from natural mineral oil
which has been
catalytically hydrogenated under high pressure and isomerized and also
deparaffinized).
Likewise suitable are mixtures of the abovementioned mineral carrier oils.
Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins
or
polyinternalolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic
polyetheramines,
alkylphenol-started polyethers, alkylphenol-started polyetheramines and
carboxylic esters of
long-chain alkanols.
Date Recue/Date Received 2020-12-09
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Examples of suitable polyolefins are olefin polymers having Mn = 400 to 1800,
in particular
based on polybutene or polyisobutene (hydrogenated or unhydrogenated).
Examples of suitable polyethers or polyetheramines are preferably compounds
comprising
polyoxy-C2- to C4-alkylene moieties which are obtainable by reacting C2- to
C60-alkanols, C6-
to C30-alkanediols, mono- or di-C2- to C30-alkylamines, Ci- to C30-
alkylcyclohexanols or Ci- to
C30-alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide
and/or butylene
oxide per hydroxyl group or amino group, and, in the case of the
polyetheramines, by
subsequent reductive amination with ammonia, monoamines or polyamines. Such
products
are described more particularly in EP-A 310 875, EP-A 356 725, EP-A 700 985
and US-A 4
877 4,877,416. For example, the polyetheramines used may be poly-C2- to C6-
alkylene oxide
amines or functional derivatives thereof. Typical examples thereof are
tridecanol butoxylates
or isotridecanol butoxylates, isononylphenol butoxylates and also
polyisobutenol butoxylates
and propoxylates, and also the corresponding reaction products with ammonia.
Examples of carboxylic esters of long-chain alkanols are more particularly
esters of mono-,
di- or tricarboxylic acids with long-chain alkanols or polyols, as described
more particularly in
DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or
aromatic acids;
particularly suitable ester alcohols or ester polyols are long-chain
representatives having, for
example, 6 to 24 carbon atoms. Typical representatives of the esters are
adipates, phthalates,
isophthalates, terephthalates and trimellitates of isooctanol, isononanol,
isodecanol and
isotridecanol, for example di(n- or isotridecyl) phthalate.
Further suitable carrier oil systems are described, for example, in DE-A 38 26
608, DE-A 41
42241, DE-A43 09074, EP-A452 328 and EP-A 548 617.
Examples of particularly suitable synthetic carrier oils are alcohol-started
polyethers having
about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and
especially 15 to 30 C3-
to C6-alkylene oxide units, for example propylene oxide, n-butylene oxide and
isobutylene
oxide units, or mixtures thereof, per alcohol molecule. Nonlimiting examples
of suitable starter
alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in
which the long-
chain alkyl radical is especially a straight-chain or branched C6- to C18-
alkyl radical. Particular
examples include tridecanol and nonylphenol. Particularly preferred alcohol-
started
polyethers are the reaction products (polyetherification products) of
monohydric aliphatic C6-
Date Recue/Date Received 2020-12-09
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to C18-alcohols with C3- to C6-alkylene oxides. Examples of monohydric
aliphatic C6-C18-
alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol,
decanol,
3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol,
pentadecanol,
hexadecanol, octadecanol and the constitutional and positional isomers
thereof. The alcohols
can be used either in the form of the pure isomers or in the form of technical
grade mixtures.
A particularly preferred alcohol is tridecanol. Examples of C3- to C6-alkylene
oxides are
propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-
butylene oxide,
2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and
hexylene oxide.
Particular preference among these is given to C3- to C4-alkylene oxides, i.e.
propylene oxide
such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-
butylene
oxide and isobutylene oxide. Especially butylene oxide is used.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, as
described in DE-A 10
102 913.
Particular carrier oils are synthetic carrier oils, particular preference
being given to the
above-described alcohol-started polyethers.
The carrier oil or the mixture of different carrier oils is added to the fuel
in an amount of
preferably 1 to 1000 ppm by weight, more preferably of 10 to 500 ppm by weight
and
especially of 20 to 100 ppm by weight.
B3) Cold flow improvers
Suitable cold flow improvers are in principle all organic compounds which are
capable of
improving the flow performance of middle distillate fuels or diesel fuels
under cold conditions.
For the intended purpose, they must have sufficient oil solubility. More
particularly, useful cold
flow improvers for this purpose are the cold flow improvers (middle distillate
flow improvers,
MDFIs) typically used in the case of middle distillates of fossil origin, i.e.
in the case of
.. customary mineral diesel fuels. However, it is also possible to use organic
compounds which
partly or predominantly have the properties of a wax antisettling additive
(WASA) when used
in customary diesel fuels. They can also act partly or predominantly as
nucleators. It is also
possible to use mixtures of organic compounds effective as MDFIs and/or
effective as WASAs
and/or effective as nucleators.
Date Recue/Date Received 2020-12-09
25
The cold flow improver is typically selected from
(K1) copolymers of a C2- to C40-olefin with at least one further ethylenically
unsaturated
monomer;
(K2) comb polymers;
(K3) polyoxyalkylenes;
(K4) polar nitrogen compounds;
(K5) sulfocarboxylic acids or sulfonic acids or derivatives thereof; and
(K6) poly(meth)acrylic esters.
It is possible to use either mixtures of different representatives from one of
the particular
classes (K1) to (K6) or mixtures of representatives from different classes
(K1) to (K6).
Suitable C2- to C40-olefin monomers for the copolymers of class (K1) are, for
example, those
having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably
1 or 2 carbon-
carbon double bonds, especially having one carbon-carbon double bond. In the
latter case,
the carbon-carbon double bond may be arranged either terminally (a-olefins) or
internally.
However, preference is given to a-olefins, particular preference to a-olefins
having 2 to 6
carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and in
particular
ethylene.
In the copolymers of class (K1), the at least one further ethylenically
unsaturated monomer is
preferably selected from alkenyl carboxylates, (meth)acrylic esters and
further olefins.
When further olefins are also copolymerized, they are preferably higher in
molecular weight
than the abovementioned C2- to C40-olefin base monomer. When, for example, the
olefin base
monomer used is ethylene or propene, suitable further olefins are especially
C10- to C40-a-
olefins. Further olefins are in most cases only additionally copolymerized
when monomers
with carboxylic ester functions are also used.
Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid
with C1- to C20-
alkanols, especially C1- to Curalkanols, in particular with methanol, ethanol,
propanol,
isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol,
hexanol, heptanol,
octanol, 2-ethylhexanol, nonanol and decanol, and structural isomers thereof.
Date Recue/Date Received 2020-12-09
26
Suitable alkenyl carboxylates are, for example, C2- to Cia-alkenyl esters, for
example the vinyl
and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose
hydrocarbon
radical may be linear or branched. Among these, preference is given to the
vinyl esters.
Among the carboxylic acids with a branched hydrocarbon radical, preference is
given to those
whose branch is in the a position to the carboxyl group, and the a-carbon atom
is more
preferably tertiary, i.e. the carboxylic acid is what is called a
neocarboxylic acid. However, the
hydrocarbon radical of the carboxylic acid is preferably linear.
Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate,
vinyl butyrate,
vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl
neononanoate, vinyl
neodecanoate and the corresponding propenyl esters, preference being given to
the vinyl
esters. A particularly preferred alkenyl carboxylate is vinyl acetate; typical
copolymers of
group (K1) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs"),
which are
some of the most frequently used.
Ethylene-vinyl acetate copolymers usable particularly advantageously and the
preparation
thereof are described in WO 99/29748.
Suitable copolymers of class (K1) are also those which comprise two or more
different alkenyl
carboxylates in copolymerized form, which differ in the alkenyl function
and/or in the
carboxylic acid group. Likewise suitable are copolymers which, as well as the
alkenyl
carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic
ester in
copolymerized form.
Terpolymers of a C2- to C40-a-olefin, a Ci- to C20-alkyl ester of an
ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a C2- to C14-alkenyl ester
of a saturated
monocarboxylic acid having 2 to 21 carbon atoms are also suitable as
copolymers of class
(K1). Terpolymers of this kind are described in WO 2005/054314. Atypical
terpolymer of this
kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.
The at least one or the further ethylenically unsaturated monomer(s) are
copolymerized in the
copolymers of class (K1) in an amount of preferably 1 to 50% by weight,
especially 10 to 45%
by weight and in particular 20 to 40% by weight, based on the overall
copolymer. The main
proportion in terms of weight of the monomer units in the copolymers of class
(K1) therefore
originates generally from the C2- to C40 base olefins.
Date Recue/Date Received 2020-12-09
27
The copolymers of class (K1) preferably have a number-average molecular weight
Mn of 1000
to 20 000, more preferably of 1000 to 10 000 and especially of 1000 to 8000.
Typical comb polymers of component (K2) are, for example, obtainable by the
copolymerization of maleic anhydride or fumaric acid with another
ethylenically unsaturated
monomer, for example with an a-olefin or an unsaturated ester, such as vinyl
acetate, and
subsequent esterification of the anhydride or acid function with an alcohol
having at least 10
carbon atoms. Further suitable comb polymers are copolymers of a-olefins and
esterified
comonomers, for example esterified copolymers of styrene and maleic anhydride
or esterified
copolymers of styrene and fumaric acid. Suitable comb polymers may also be
polyfumarates
or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb
polymers.
Comb polymers suitable as components of class (K2) are, for example, also
those described
in WO 2004/035715 and in "Comb-Like Polymers. Structure and Properties", N. A.
Plate and
V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974)".
Mixtures of
comb polymers are also suitable.
Polyoxyalkylenes suitable as components of class (K3) are, for example,
polyoxyalkylene
esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and
mixtures thereof.
These polyoxyalkylene compounds preferably comprise at least one linear alkyl
group,
preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms
and a
polyoxyalkylene group having a number-average molecular weight of up to 5000.
Such
polyoxyalkylene compounds are described, for example, in EP A 061 895 and also
in US 4
491 455. Particular polyoxyalkylene compounds are based on polyethylene
glycols and
polypropylene glycols having a number-average molecular weight of 100 to 5000.
Additionally
suitable are polyoxyalkylene mono- and diesters of fatty acids having 10 to 30
carbon atoms,
such as stearic acid or behenic acid.
Polar nitrogen compounds suitable as components of class (K4) may be either
ionic or
nonionic and preferably have at least one substituent, especially at least two
substituents, in
the form of a tertiary nitrogen atom of the general formula >NR7 in which R7
is a C8- to C40-
hydrocarbyl radical. The nitrogen substituents may also be quaternized, i.e.
be in cationic
form. An example of such nitrogen compounds is that of ammonium salts and/or
amides
which are obtainable by the reaction of at least one amine substituted by at
least one
hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or
with a suitable
Date Recue/Date Received 2020-12-09
28
derivative thereof. The amines preferably comprise at least one linear C8- to
C40-alkyl radical.
Primary amines suitable for preparing the polar nitrogen compounds mentioned
are, for
example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine,
tetradecylamine and the higher linear homologs; secondary amines suitable for
this purpose
are, for example, dioctadecylamine and methylbehenylamine. Also suitable for
this purpose
are amine mixtures, especially amine mixtures obtainable on the industrial
scale, such as fatty
amines or hydrogenated tallamines, as described, for example, in Ullmann's
Encyclopedia of
Industrial Chemistry, 6th Edition, "Amines, aliphatic" chapter. Acids suitable
for the reaction
are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-
dicarboxylic acid,
cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic
acid, isophthalic
acid, terephthalic acid, and succinic acids substituted by long-chain
hydrocarbon radicals.
More particularly, the component of class (K4) is an oil-soluble reaction
product of poly(C2- to
C20-carboxylic acids) having at least one tertiary amino group with primary or
secondary
amines. The poly(C2- to C20-carboxylic acids) which have at least one tertiary
amino group
and form the basis of this reaction product comprise preferably at least 3
carboxyl groups,
especially 3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic
acid units in the
polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially
acetic acid
units. The carboxylic acid units are suitably bonded to the polycarboxylic
acids, usually via
one or more carbon and/or nitrogen atoms. They are preferably attached to
tertiary nitrogen
atoms which, in the case of a plurality of nitrogen atoms, are bonded via
hydrocarbon chains.
The component of class (K4) is preferably an oil-soluble reaction product
based on poly(C2-
to C20-carboxylic acids) which have at least one tertiary amino group and are
of the general
formula Ila or Ilb
HOOC,B B_COOH
1 1
HOOC,B,N,A-N, COOH
B,
(11a)
HOOCB õ NB õCOOH
1
B,COOH (II b)
Date Recue/Date Received 2020-12-09
29
in which the variable A is a straight-chain or branched C2- to C6-alkylene
group or the moiety
of the formula III
B.. CH
HOOC 'N
1
CH2-CH2-
(III)
and the variable B is a Ci- to C19-alkylene group. The compounds of the
general formulae ha
and II b especially have the properties of a WASA.
Moreover, the preferred oil-soluble reaction product of component (K4),
especially that of the
general formula ha or Ilb, is an amide, an amide-ammonium salt or an ammonium
salt in
which no, one or more carboxylic acid groups have been converted to amide
groups.
Straight-chain or branched C2- to C6-alkylene groups of the variable A are,
for example,
1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-
butylene,
2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethy1-1,3-
propylene,
1,6-hexylene (hexamethylene) and especially 1,2-ethylene. The variable A
comprises
preferably 2 to 4 and especially 2 or 3 carbon atoms.
Ci- to C19-alkylene groups of the variable B are, for example, 1,2-ethylene,
1,3-propylene,
1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene,
tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene
and
especially methylene. The variable B comprises preferably 1 to 10 and
especially 1 to 4
carbon atoms.
The primary and secondary amines as a reaction partner for the polycarboxylic
acids to form
component (K4) are typically monoamines, especially aliphatic monoamines.
These primary
and secondary amines may be selected from a multitude of amines which bear
hydrocarbon
radicals which may optionally be bonded to one another.
These parent amines of the oil-soluble reaction products of component (K4) are
usually
secondary amines and have the general formula HN(R8)2 in which the two
variables R8 are
each independently straight-chain or branched Cio- to Cm-alkyl radicals,
especially Cia- to
C24-alkyl radicals. These relatively long-chain alkyl radicals are preferably
straight-chain or
only slightly branched. In general, the secondary amines mentioned, with
regard to their
Date Recue/Date Received 2020-12-09
30
relatively long-chain alkyl radicals, derive from naturally occurring fatty
acids and from
derivatives thereof. The two R8 radicals are preferably the same.
The secondary amines mentioned may be bonded to the polycarboxylic acids by
means of
amide structures or in the form of the ammonium salts; it is also possible for
only a portion to
be present as amide structures and another portion as ammonium salts.
Preferably only few,
if any, free acid groups are present. The oil-soluble reaction products of
component (K4) are
preferably present completely in the form of the amide structures.
Typical examples of such components (K4) are reaction products of
nitrilotriacetic acid, of
ethylenediaminetetraacetic acid or of propylene-1,2-diaminetetraacetic acid
with in each case
0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per carboxyl
group, of
dioleylamine, dipalmitamine, dicocoamine, distearylamine, dibehenylamine or
especially
ditallowamine. A particularly preferred component (K4) is the reaction product
of 1 mol of
ethylenediaminetetraacetic acid and 4 mol of hydrogenated ditallowamine.
Further typical examples of component (K4) include the N,N-dialkylammonium
salts of
.. 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mol of
phthalic
anhydride and 2 mol of ditallowamine, the latter being hydrogenated or
unhydrogenated, and
the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a
dialkylamine, for
example ditallowamine and/or tallowamine, the latter two being hydrogenated or
unhydrogenated.
Further typical structure types for the component of class (K4) are cyclic
compounds with
tertiary amino groups or condensates of long-chain primary or secondary amines
with
carboxylic acid-containing polymers, as described in WO 93/18115.
Sulfocarboxylic acids, sulfonic acids or derivatives thereof suitable as cold
flow improvers of
the component of class (K5) are, for example, the oil-soluble carboxamides and
carboxylic
esters of ortho-sulfobenzoic acid, in which the sulfonic acid function is
present as a sulfonate
with alkyl-substituted ammonium cations, as described in EP-A 261 957.
Poly(meth)acrylic esters suitable as cold flow improvers of the component of
class (K6) are
either homo- or copolymers of acrylic and methacrylic esters. Preference is
given to
copolymers of at least two different (meth)acrylic esters which differ with
regard to the
Date Recue/Date Received 2020-12-09
31
esterified alcohol. The copolymer optionally comprises another different
olefinically
unsaturated monomer in copolymerized form. The weight-average molecular weight
of the
polymer is preferably 50 000 to 500 000. A particularly preferred polymer is a
copolymer of
methacrylic acid and methacrylic esters of saturated C14- and C15-alcohols,
the acid groups
having been neutralized with hydrogenated tallamine. Suitable
poly(meth)acrylic esters are
described, for example, in WO 00/44857.
The cold flow improver or the mixture of different cold flow improvers is
added to the middle
distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm
by weight, more
preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm
by weight
and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by
weight.
B4) Lubricity improvers
Suitable lubricity improvers or friction modifiers are based typically on
fatty acids or fatty acid
esters. Typical examples are tall oil fatty acid, as described, for example,
in WO 98/004656,
and glyceryl monooleate. The reaction products, described in US 6 743 266 B2,
of natural or
synthetic oils, for example triglycerides, and alkanolamines are also suitable
as such lubricity
im provers.
B5) Corrosion inhibitors
Suitable corrosion inhibitors are, for example, succinic esters, in particular
with polyols, fatty
acid derivatives, for example oleic esters, oligomerized fatty acids,
substituted ethanolamines,
and products sold under the trade name RC 4801 (Rhein Chemie Mannheim,
Germany) or
HiTEC 536 (Ethyl Corporation).
B6) Demulsifiers
Suitable demulsifiers are, for example, the alkali metal or alkaline earth
metal salts of alkyl-
substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline
earth metal
salts of fatty acids, and also neutral compounds such as alcohol alkoxylates,
e.g. alcohol
ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-
pentylphenol
ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide
(EO) and
Date Recue/Date Received 2020-12-09
32
propylene oxide (PO), for example including in the form of EO/PO block
copolymers,
polyethyleneimines or else polysiloxanes.
B7) Dehazers
Suitable dehazers are, for example, alkoxylated phenol-formaldehyde
condensates, for
example the products available under the trade names NALCO 7D07 (Nalco) and
TOLAD
2683 (Petrolite).
B8) Antifoams
Suitable antifoams are, for example, polyether-modified polysiloxanes, for
example the
products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907
(Dow
Corning) and RHODOSIL (Rhone Poulenc).
B9) Cetane number improvers
Suitable cetane number improvers are, for example, aliphatic nitrates such as
2-ethylhexyl
nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
B10) Antioxidants
.. Suitable antioxidants are, for example substituted phenols, such as 2,6-di-
tert-butylphenol
and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines such as N,N'-di-
sec-butyl-p-
phenylenediamine.
B11) Metal deactivators
Suitable metal deactivators are, for example, salicylic acid derivatives such
as N,N'-
disalicylidene-1,2-propanediamine.
B12) Solvents
Suitable solvents are, for example, nonpolar organic solvents such as aromatic
and aliphatic
hydrocarbons, for example toluene, xylenes, white spirit and products sold
under the trade
names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), and also
polar
organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and
isotridecanol.
Date Recue/Date Received 2020-12-09
33
Such solvents are usually added to the diesel fuel together with the
aforementioned additives
and coadditives, which they are intended to dissolve or dilute for better
handling.
C) Fuels
The inventive additive is outstandingly suitable as a fuel additive and can be
used in principle
in any fuels. It brings about a whole series of advantageous effects in the
operation of internal
combustion engines with fuels. Preference is given to using the inventive
quaternized additive
in middle distillate fuels, especially diesel fuels.
The present invention therefore also provides fuels, especially middle
distillate fuels, with a
content of the inventive quaternized additive which is effective as an
additive for achieving
advantageous effects in the operation of internal combustion engines, for
example of diesel
engines, especially of direct injection diesel engines, in particular of
diesel engines with
common rail injection systems. This effective content (dosage) is generally 10
to 5000 ppm
by weight, preferably 20 to 1500 ppm by weight, especially 25 to 1000 ppm by
weight, in
particular 30 to 750 ppm by weight, based in each case on the total amount of
fuel.
Middle distillate fuels such as diesel fuels or heating oils are preferably
mineral oil raffinates
which typically have a boiling range from 100 to 400 C. These are usually
distillates having
a 95% point up to 360 C or even higher. These may also be what is called
"ultra low sulfur
diesel" or "city diesel", characterized by a 95% point of, for example, not
more than 345 C
and a sulfur content of not more than 0.005% by weight or by a 95% point of,
for example,
285 C and a sulfur content of not more than 0.001% by weight. In addition to
the mineral
middle distillate fuels or diesel fuels obtainable by refining, those
obtainable by coal
gasification or gas liquefaction ["gas to liquid" (GTL) fuels] or by biomass
liquefaction
["biomass to liquid" (BTL) fuels] are also suitable. Also suitable are
mixtures of the
aforementioned middle distillate fuels or diesel fuels with renewable fuels,
such as biodiesel
or bioethanol.
The qualities of the heating oils and diesel fuels are laid down in detail,
for example, in DIN
51603 and EN 590 (cf. also Ullmann's Encyclopedia of Industrial Chemistry, 5th
edition,
Volume Al2, p. 617 ff.).
Date Recue/Date Received 2020-12-09
34
In addition to the use thereof in the abovementioned middle distillate fuels
of fossil, vegetable
or animal origin, which are essentially hydrocarbon mixtures, the inventive
quaternized
additive can also be used in mixtures of such middle distillates with biofuel
oils (biodiesel).
Such mixtures are also encompassed by the term "middle distillate fuel" in the
context of the
present invention. They are commercially available and usually comprise the
biofuel oils in
minor amounts, typically in amounts of 1 to 30% by weight, especially of 3 to
10% by weight,
based on the total amount of middle distillate of fossil, vegetable or animal
origin and biofuel
oil.
Biofuel oils are generally based on fatty acid esters, preferably essentially
on alkyl esters of
fatty acids which derive from vegetable and/or animal oils and/or fats. Alkyl
esters are typically
understood to mean lower alkyl esters, especially C1-C4-alkyl esters, which
are obtainable by
transesterifying the glycerides which occur in vegetable and/or animal oils
and/or fats,
especially triglycerides, by means of lower alcohols, for example ethanol or
in particular
methanol ("FAME"). Typical lower alkyl esters based on vegetable and/or animal
oils and/or
fats, which find use as a biofuel oil or components thereof, are, for example,
sunflower methyl
ester, palm oil methyl ester ("PME"), soya oil methyl ester ("SME") and
especially rapeseed
oil methyl ester ("RME").
The middle distillate fuels or diesel fuels are more preferably those having a
low sulfur content,
i.e. having a sulfur content of less than 0.05% by weight, preferably of less
than 0.02% by
weight, more particularly of less than 0.005% by weight and especially of less
than 0.001%
by weight of sulfur.
Useful gasoline fuels include all commercial gasoline fuel compositions. One
typical
representative which shall be mentioned here is the Eurosuper base fuel to EN
228, which is
customary on the market. In addition, gasoline fuel compositions of the
specification
according to WO 00/47698 are also possible fields of use for the present
invention.
The inventive quaternized additive is especially suitable as a fuel additive
in fuel compositions,
especially in diesel fuels, for overcoming the problems outlined at the outset
in direct injection
diesel engines, in particular in those with common rail injection systems.
Date Recue/Date Received 2020-12-09
35
The invention is now illustrated in detail by the working examples which
follow. Especially the
test methods specified hereinafter form part of the general disclosure of the
application and
are not restricted to the specific working examples.
Experimental:
Reagents used:
N-methyl-N,N-ditallowamine: Armeene M2HT from Akzo Nobel, CAS 61788-63-4,
total
amine value 103-110 mg KOH/g.
Solvent Naphtha Heavy from Exxon Mobil, CAS 64742-94-5.
dimethyl oxalate from Aldrich, CAS 553-90-2
lauric acid from Aldrich, CAS 143-07-7
3,5,5-trimethylhexanoic acid from BASF, CAS 3302-10-1
methyl salicylate from Aldrich, CAS 119-36-8
2-ethylhexanol from BASF, CAS 104-76-7
acetic acid from Aldrich, CAS 64-19-7
A. General test methods
Engine test
1. XUD9 test - determination of flow restriction
The procedure was according to the standard stipulations of CEC F-23-1-01.
2. DW10 test - determination of power loss as a result of injector deposits in
the common rail
diesel engine
2.1. DW10-KC - keep-clean test
The keep-clean test is based on CEC test procedure F-098-08 Issue 5. This is
done using
the same test setup and engine type (PEUGEOT DW10) as in the CEC procedure.
Change and special features:
In the tests, cleaned injectors were used. The cleaning time in the ultrasound
bath in water +
10% Superdecontamine (Intersciences, Brussels) at 60 C was 4 h.
Date Recue/Date Received 2020-12-09
36
Test run times:
The test run time was 12 h without shutdown phases. The one-hour test cycle
from CEC
F-098-08, shown in figure 2, was run through 12 times.
Performance determination:
The initial power PO,KC [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot. The procedure
is described in
Issue 5 of the test procedure (CEC F-98-08). This is done using the same test
setup and the
PEUGEOT DW10 engine type.
The final performance (Pend,KC) is determined in the 12th cycle in stage 12
(see table, figure
2). Here too, the operation point is full load 4000/min. Pend,KC [kW] is
calculated from the
torque measured.
The power loss in the KC test is calculated as follows:
Powerloss ,KC [%] = (1 Pend, PO,KC KC)
____________________________________________________ *100
2.2. DW10 dirty-up clean-up (DU-CU)
The DU-CU test is based on CEC test procedure F-098-08 Issue 5. The procedure
is
described in Issue 5 of the test procedure (CEC F-98-08). This is done using
the same test
setup and the PEUGEOT DW10 engine type.
The DU-CU test consists of two individual tests which are run in succession.
The first test
serves to form deposits (DU), the second to remove the deposits (CU). After
the DU, the
power loss is determined. After the end of the DU run, the engine is not
operated for at least
8 hours and is cooled to ambient temperature. Thereafter, the CU fuel is used
to start the CU
without deinstalling and cleaning the injectors. The deposits and power loss
ideally decline
over the course of the CU test.
Change and special features:
Cleaned injectors were installed in the engine prior to each DU test. The
cleaning time in the
ultrasound bath at 60 C, in water + 10% Superdecontamine (Intersciences,
Brussels), was
4 h.
Date Recue/Date Received 2020-12-09
37
Test run times:
The test run time was 12 h for the DU and 12 h for the CU. The engine was
operated in the
DU and CU tests without shutdown phases.
The one-hour test cycle from CEC F-098-08, shown in figure 2, was run through
12 times in
each case.
Performance determination:
The initial power PO,du [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot. The procedure
is likewise
described in Issue 5 of the test procedure.
The final performance (Pend,du) is determined in the 12th cycle in stage 12
(see table above).
Here too, the operation point is full load 4000/min. Pend,du [kW] is
calculated from the torque
measured.
The power loss in the DU is calculated as follows:
Powerloss,du [ /0] = (1 Pend' du)* 100
PO, du
Clean-up
The initial power PO,cu [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot in the CU. The
procedure is
likewise described in Issue 5 of the test procedure.
The final performance (Pend,cu) is determined in the 12th cycle in stage 12
(see table, figure
.. 2). Here too, the operation point is full load 4000/min. Pend,cu [kVV] is
calculated from the
torque measured.
The power loss in the CU test is calculated as follows (negative number for
the power loss in
the CU test means an increase in performance)
(Pend, du ¨ pend, cu)
Powerloss (DU,CU)[%] = __________________________________ * 100
PO, du
Date Recue/Date Received 2020-12-09
38
The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To
artificially induce
the formation of deposits at the injectors, 1 ppm by weight of zinc in the
form of a zinc
didodecanoate solution was added thereto.
3. IDID test - determination of additive action against internal injector
deposits
.. The formation of deposits within the injector was characterized on the
basis of the deviations
in the exhaust gas temperatures of the cylinders at the cylinder outlet when
the DW10 engine
is cold-started.
To promote the formation of deposits, 1 mg/I of sodium salt of an organic
acid, 20 mg/I of
dodecenylsuccinic acid and 10 mg/I of water were added to the fuel.
.. The test is conducted as a dirty-up clean-up test (DU-CU).
DU-CU is based on CEC test procedure F-098-08 Issue 5.
The DU-CU test consists of two individual tests which are run in succession.
The first test
serves to form deposits (DU), the second to remove the deposits (CU).
After the DU run, after a rest phase of at least eight hours, a cold start of
the engine is
.. conducted, followed by idling for 10 minutes.
Thereafter, the CU fuel is used to start the CU without deinstalling and
cleaning the injectors.
After the CU run over 8 h, after a rest phase of at least eight hours, a cold
start of the engine
is conducted, followed by idling for 10 minutes. The evaluation is effected by
the comparison
of the temperature profiles for the individual cylinders after the cold start
in the DU and CU
.. runs.
The IDID test indicates the formation of internal deposits in the injector.
The characteristic
used in this test is the exhaust gas temperature of the individual cylinders.
In an injector
system without IDIDs, the exhaust gas temperatures of the cylinders increase
homogeneously. In the presence of IDIDs, the exhaust gas temperatures of the
individual
cylinders do not increase homogeneously and deviate from one another.
Date Recue/Date Received 2020-12-09
39
The temperature sensors are beyond the cylinder head outlet in the exhaust gas
manifold.
Significant deviation of the individual cylinder temperatures (e.g. > 20 C)
indicates the
presence of internal injector deposits (IDIDs).
The tests (DU and CU) are each conducted with run time 8 h. The one-hour test
cycle from
CEC F-098-08 (see figure 3) is run through 8 times in each case. In the event
of deviations
of the individual cylinder temperatures of greater than 45 C from the mean for
all 4 cylinders,
the test is stopped early.
Alteration and special features: cleaned injectors were installed prior to the
start of each DU
test. The cleaning time in the ultrasound bath at 60 C, water + 10%
Superdecontamine, was
4h.
B. Preparation examples:
Preparation example 1: N,N-dimethyl-N,N-ditallowammonium methyloxalate was
synthesized on the basis of EP 2 033 945
N-Methyl-N,N-ditallowamine (90 g) is admixed with dimethyl oxalate (90 g) and
lauric acid
(1.8 g). The reaction mixture is heated to 120 C and stirred at this
temperature for 4 h.
Subsequently, excess dimethyl oxalate is removed at 130 C under reduced
pressure with the
aid of a rotary evaporator. This gives 110.8 g of the product as a white wax.
1H NMR (CDCI3)
confirms the quaternization.
Preparation example 2: N,N-dimethyl-N,N-ditallowammonium salicylate
N-Methyl-N,N-ditallowamine (80 g) is admixed with methyl salicylate (45.4 g)
and 3,5,5-
trimethylhexanoic acid (0.8 g). The reaction mixture is heated to 160 C and
stirred at this
temperature for 4 h. After cooling to room temperature, 124 g of the product
are obtained as
a white wax. 1H NMR (CDCI3) confirms the quaternization.
Preparation example 3: N-methyl-N-(2-hydroxypropyI)-N,N-ditallowammonium
acetate
In a 2 I autoclave, a solution of N-methyl-N,N-ditallowamine (250 g) in 2-
ethylhexanol (250 g)
is admixed with acetic acid (100%, 33.5 g). This is followed by purging three
times with N2,
establishment of an initial pressure of approx. 1.3 bar of N2 and an increase
in the temperature
Date Recue/Date Received 2020-12-09
40
to 50 C. Propylene oxide (54 g) is metered in such that the temperature
remains between
45-55 C. This is followed by stirring at 50 C for 10 h, cooling to 25 C,
purging with N2 and
emptying of the reactor. The product is degassed on a rotary evaporator at 80
C and 20 mbar
for 3 h. This gives 549.4 g of the product in 2-ethylhexanol. 1H NMR (CDC13)
confirms the
quaternization. The sample is adjusted to an active ingredient content of 38%
by addition of
Solvent Naphtha Heavy.
C. Use examples:
In the use examples which follow, the additives are used either as a pure
substance (as
synthesized in the above preparation examples) or in the form of an additive
package.
Use example 1: determination of additive action on the formation of deposits
in diesel
engine injection nozzles
a) XUD9 tests
Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The results are summarized in table 1.
Table 1: Results of the XUD9 tests
Ex. Reference Dosage Flow restriction
ppm active 0.1 mm needle
stroke
Fol
#1 according to 30 8.4
preparation example 1
#2 according to 15 22.4
preparation example 1
b) DW10 test
The table below shows the results of the determinations of the relative power
loss at 4000
rpm after 12 hours of sustained operation without interruption. The value PO
gives the power
after 10 minutes and the value Pend the power at the end of the measurement:
Date Recue/Date Received 2020-12-09
41
The test results are shown in table 2.
Table 2: Results of the DW10 test
Dose Power loss Power loss Power loss
Additive
[mg/kg] KC DU DU-CU
base value 0 4.1%
according to preparation
100 0.4%
example 1, keep clean
according to preparation
100 -4.9%
example 1, clean-up
base value 0 3.8%
according to preparation
100 -0.4%
example 2, keep clean
It is found that the inventive additives according to preparation examples 1
and 2 have
improved action compared to the base value.
c) Action against internal injector deposits (IDID)
Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The test results are shown in appended figures 1 and 2.
Figure 1 shows a measurement of the exhaust gas temperatures of the cylinders
in the case
of use of a fuel without additive; large deviations in the temperature are
caused by internal
injector deposits.
Figure 2 shows the exhaust gas temperatures measured in the same cylinders
after treatment
with the inventive additive from preparation example 3, dosage 394 mg/kg.
The measurements illustrate the action of the inventive additive for
dissolution of internal
injector deposits. The falls in the exhaust gas temperature caused by the
internal injector
deposits (fig. 1, cylinders 1 and 4) can be eliminated again by the inventive
additive.
Reference is made explicitly to the disclosure of the publications cited
herein.
Date Recue/Date Received 2020-12-09
