Note: Descriptions are shown in the official language in which they were submitted.
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Quaternized nitrogen compounds and use thereof as additives in fuels and
lubricants
The present invention relates to novel quaternized nitrogen compounds, to the
preparation
thereof and to the use thereof as a fuel and lubricant additive, more
particularly as a
detergent additive, to additive packages which comprise these compounds; and
to fuels
and lubricants thus additized. The present invention further relates to the
use of these
quaternized nitrogen compounds as a fuel additive for reducing or preventing
deposits in
the injection systems of direct-injection diesel engines, especially in common-
rail injection
systems, for reducing the fuel consumption of direct-injection diesel engines,
especially of
diesel engines with common-rail injection systems, and for minimizing power
loss in direct-
injection diesel engines, especially in diesel engines with common-rail
injection systems.
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 to inject 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
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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 combusted, but instead evaporated 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 NON.
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
(NO), carbon monoxide (CO) and especially of particulates (soot). This makes
it possible,
for example, that engines equipped with common-rail injection systems can 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
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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 for prevention of sludge formation. More particularly, for example, the
reaction of
polyisobutylsuccinic anhydride (PIBSA) 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. For
quaternization, preference is given to using alkyl halides. Also mentioned are
organic 02-
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 02-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 Ca-C40-alkyl radical with a CI-Ca-
alkyl ester of
specific carboxylic acids. Examples of such carboxylic esters are dimethyl
oxalate,
dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Applications other
than that
of improving 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
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hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid,
especially 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 alkylene oxides 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).
It was therefore an object of the present invention to provide improved
quaternized fuel
additives, especially based on hydrocarbyl-substituted polycarboxylic acid
compounds,
which no longer have the disadvantages of the prior art mentioned.
Brief description of the invention:
It has now been found that, surprisingly, the above object is achieved by
providing specific
quaternized nitrogen compounds and fuel and lubricant compositions additized
therewith.
Surprisingly, the inventive additives thus prepared are superior in several
ways to the prior
art additives prepared in a conventional manner: they have low toxicity
(caused by the
specific selection of the quaternizing agent, burn ashlessly, exhibit a high
content of
quaternized product, and allow an economic reaction regime in the preparation
thereof,
and surprisingly have improved handling properties, such as especially
improved solubility,
such as especially in diesel performance additive packages. At the same time,
the
inventive additives exhibit improved action with regard to prevention of
deposits in diesel
engines, as especially illustrated by the use examples appended.
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Detailed description of the invention:
Al) Specific embodiments
5 The present invention relates especially to the following specific
embodiments:
1. A
fuel or lubricant composition, especially fuel 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
a. reacting a high molecular weight hydrocarbyl-substituted polycarboxylic
acid compound with a compound comprising at least one oxygen or nitrogen group
reactive (especially capable of addition or condensation) with the
polycarboxylic acid, and
comprising at least one quaternizable amino group, to obtain a quaternizable
hydrocarbyl-
substituted polycarboxylic acid compound (by addition or condensation), and
b. subsequent reaction thereof with a quaternizing agent which converts the
at
least one hereafter quaternizable, for example tertiary, amino group to a
quaternary
ammonium group, said 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).
2. A
fuel or lubricant composition, especially fuel 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 high molecular weight hydrocarbyl-substituted
polycarboxylic acid
compound comprising at least one quaternizable amino group with a quaternizing
agent
which converts the at least one hereafter quaternizable, for example tertiary,
amino group
to a quaternary ammonium group,
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said 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).
3. The fuel
composition according to either of the preceding claims, wherein about 1.1
to about 2.0 or about 1.25 to about 2.0 equivalents, for example 1.3, 1.4,
1.5, 1.6, 1.7, 1.8
or 1.9 equivalents, of quaternizing agent are used per equivalent of
quaternizable tertiary
nitrogen atom. By increasing the proportion of quaternizing agent within the
range claimed,
distinct improvements in product yields can be achieved.
4. The fuel
composition according to any of the preceding claims, wherein the
hydrocarbyl-substituted polycarboxylic acid compound is a
polyisobutenylsuccinic acid or
an anhydride thereof, said acid having a bismaleation level of equal to or
less than about
20% or equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9,
8, 7, 6, 5,4,
3, 2, 1 or 0.1%.
Lower levels of bismaleation can contribute to a distinct improvement in the
solubility of the
additive and/or compatibility of the constituents in the formulation of
additive packages.
5. The fuel
or lubricant composition, especially fuel 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 especially 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 R1OC(0)-, in which R1 is as defined
above
and R3 is H or R1, where the substituent is especially OH. More particularly,
the
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quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate
or methyl
salicylate.
6. The fuel or lubricant composition, especially fuel composition,
according to any of
the preceding embodiments, 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 hydrocarbylene (such as especially C1-C7-alkylene or C2-C7-alkenylene).
7. The fuel or lubricant composition, especially fuel composition,
according to any of
the preceding embodiments, wherein the quaternized nitrogen compound has a
number-
average molecular weight in the range from 400 to 5000, especially 800 to 3000
or 900 to
1500.
8. The fuel or lubricant composition, especially fuel composition,
according to any of
the preceding embodiments, wherein the quaternizing agent is selected from
alkyl
salicylates, dialkyl phthalates and dialkyl oxalates; particular mention
should be made of
alkyl salicylates, especially lower alkyl salicylates, such as methyl, ethyl
and n-propyl
salicylates.
9. The
fuel or lubricant composition, especially fuel composition, according to
embodiment 1, wherein the compound which is reactive (capable of addition or
condensation) with the polycarboxylic acid and comprises an oxygen or nitrogen
group
and at least one quaternizable amino group is selected from
a.
hydroxyalkyl-substituted mono- or polyamines having at least one
quaternizable primary, secondary or tertiary amino group;
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b. straight-chain or branched, cyclic, heterocyclic, aromatic or
nonaromatic
polyamines having at least one primary or secondary amino group and having at
least one
quaternizable primary, secondary or tertiary amino group;
c. piperazines,
and particular mention should be made of group a.
10. The fuel or lubricant composition according to embodiment 9,
wherein the
compound which is reactive, especially capable of addition or condensation,
with the
polycarboxylic acid and comprises an oxygen or nitrogen group and at least one
quaternizable amino group is selected from
a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and
hydroxyalkyl-substituted primary, secondary or tertiary diamines,
b. straight-chain or branched aliphatic diamines having two primary amino
groups; di- or polyamines having at least one primary and at least one
secondary amino
group; di- or polyamines having at least one primary and at least one tertiary
amino group;
aromatic carbocyclic diamines having two primary amino groups; aromatic
heterocyclic
polyamines having two primary amino groups; aromatic or nonaromatic
heterocycles
having one primary and one tertiary amino group;
and particular mention should be made of group a.
11. The fuel composition according to any of the preceding
embodiments, selected
from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing
gasoline fuels.
12. The fuel or lubricant composition, especially fuel composition,
according to any of
.. the preceding embodiments, wherein the hydrocarbyl-substituted
polycarboxylic acid
compound is a polyisobutenylsuccinic acid or an anhydride (PIBSA) thereof,
said acid
having a low bismaleation level, especially 10% or less than 10%, for example
2 to 9 or 3
to 7%. More particularly, such PIBSAs are derived from HR-PIB with an Mn in
the range
from about 400 to 3000.
More particularly, the above compositions are fuel compositions, in particular
diesel fuels.
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13. The reaction product obtainable by a process as defined in any of the
preceding
embodiments, especially according to embodiment 3, 4, 5, 6 and in particular
embodiment
8, 9 or 10, or quaternized nitrogen compound obtained from the reaction
product by partial
or full purification.
In a particular configuration (A) of the invention, quaternized reaction
products which are
prepared proceeding from polyisobutenylsuccinic acid or an anhydride thereof
are
provided, this compound having a bismaleation level of equal to or less than
about 20% or
equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 7,
6, 5, 4, 3, 2, 1,
or 0.1%. This polyisobutenylsuccinic acid compound is reacted (especially by
addition or
condensation) with a compound comprising at least one oxygen or nitrogen group
reactive
(addable or condensable) with the polyisobutenylsuccinic acid compound and
containing
at least one quaternizable amino group, and then quaternized.
In a particular configuration (B) of the invention, quaternized reaction
products which are
obtained by quaternization using an excess of quaternizing agent are provided.
More
particularly, about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents,
for example 1.3,
1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, equivalents of quaternizing agent are used per
equivalent of
quaternizable tertiary nitrogen atoms. Particularly useful quaternizing agents
are those of
the formula (1), especially 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.
In a further particular configuration (C), configurations (A) and (B) are
combined, i.e. the
quaternizable compounds prepared from the above polyisobutenylsuccinic acid
compounds according to configuration (A) are quaternized according to
configuration (B).
14. A
process for preparing a quaternized nitrogen compound according to
embodiment 13,
comprising the reaction of a quaternizable hydrocarbyl-substituted
polycarboxylic acid
compound comprising at least one tertiary quaternizable amino group with a
quaternizing
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agent which converts the at least one tertiary amino group to a quaternary
ammonium
group,
said 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
5 polycarboxylic acid (especially dicarboxylic acid).
15. The use of a reaction product or of a quaternized nitrogen compound
according
to embodiment 13 or of a compound prepared according to embodiment 14 as a
fuel
additive or lubricant additive, especially fuel additive, especially diesel
fuel additive.
16. The use according to embodiment 15 as an additive for reducing the fuel
consumption of direct-injection diesel engines, especially of diesel engines
with common-
rail injection systems, as determined, for example, in an XUD9 test to CEC-F-
23-01,
and/or for minimizing power loss in direct-injection diesel engines,
especially in diesel
engines with common-rail injection systems, as determined, for example, in a
DW10 test
based on CEC-F-098-08.
17. The use according to embodiment 15 as a gasoline fuel additive for
reducing the
level of deposits in the intake system of a gasoline engine, such as
especially DISI (direct
injection spark ignition) and PFI (port fuel injector) engines.
18. The use according to embodiment 15 as a diesel fuel additive,
especially as a
cold flow improver, as a wax antisettling additive (WASA) or as an additive
for reducing the
level of and/or preventing deposits in the intake systems, such as especially
the internal
diesel injector deposits (IDIDs), and/or valve sticking in direct-injection
diesel engines,
especially in common-rail injection systems.
19. An additive concentrate comprising, in combination with further diesel
fuel or
gasoline fuel additives, especially diesel fuel additives, at least one
quaternized nitrogen
compound as defined in embodiment 13 or prepared according to embodiment 14.
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A2) General definitions
A "condensation" or "condensation reaction" in the context of the present
invention
describes the reaction of two molecules with elimination of a relatively small
molecule,
especially of a water molecule. When such an elimination is not detectable
analytically,
more particularly not detectable in stoichiometric amounts, and the two
molecules react
nevertheless, for example with addition, the reaction in question of the two
molecules is
"without condensation".
In the absence of statements to the contrary, the following general conditions
apply:
"Hydrocarbyl' can be interpreted widely and comprises both long-chain and
short-chain,
straight-chain and branched hydrocarbon radicals, which may optionally
additionally
comprise heteroatoms, for example 0, N, NH, S, in the chain thereof.
"Long-chain" or "high molecular weight" hydrocarbyl radicals have a number-
average
molecular weight (Mr) 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.
More
particularly, they are formed essentially from 02-6, especially 02-4, 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-02-6- or poly-
02.4-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.
Examples of particularly useful polyalkylene radicals are polyisobutenyl
radicals derived
from ''high-reactivity" polyisobutenes (HR-PIB) which are notable for a high
content of
terminal double bonds (cf., for example, also Rath et al., Lubrication Science
(1999), 11-2,
175-185). Terminal double bonds are alpha-olefinic double bonds of the type
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Polymer _________________________________
which are also referred to collectively as vinylidene double bonds. Suitable
high-reactivity
polyisobutenes are, for example, polyisobutenes which have a proportion of
vinylidene
double bonds of greater than 70 mar/0, especially greater than 80 mol% or
greater than
85 mol%. Preference is given especially to polyisobutenes which have
homogeneous
polymer structures. Homogeneous polymer structures are possessed especially by
those
polyisobutenes formed from isobutene units to an extent of at least 85% by
weight,
preferably to an extent of at least 90% by weight and more preferably to an
extent of at
least 95% by weight. Such high-reactivity polyisobutenes preferably have a
number-
average molecular weight within the abovementioned range. In addition, the
high-reactivity
polyisobutenes may have a polydispersity in the range from 1.05 to 7,
especially of about
1.1 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is
understood to
mean the quotient of weight-average molecular weight Mw divided by the number-
average
molecular weight Mn.
Particularly suitable high-reactivity polyisobutenes are, for example, the
Glissopal brands
from BASF SE, especially Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn =
550),
Glissopal 1300 (Mn = 1300) and Glissopal 2300 (Mn = 2300), and mixtures
thereof.
Other number-average molecular weights can be established in a manner known in
principle by mixing polyisobutenes of different number-average molecular
weights or by
extractive enrichment of polyisobutenes of particular molecular weight ranges.
PIBSA is prepared in a manner known in principle by reacting PIB with maleic
anhydride
(MAA), in principle forming a mixture of PIBSA and bismaleated PIBSA (BM
PIBSA, cf.
scheme 1, below), which is generally not separated but used as such in further
reactions.
The ratio of the two components to one another can be reported via the
"bismaleation
level" (BML). The BML is known per se (see also US 5,883,196). The BML can
also be
determined by the following formula:
13
BML = 100% x [(wt-%(BM PIBSA))/(wt-%(BM PIBSA)+wt-NPIBSA))]
where wt-% (X) represents the proportion by weight of component X (X = PIBSA
or BM
PIBSA) in the conversion product of PIB with MSA.
Scheme 1
o 0
o
n
0
0
PIB MSA PIBSA BM PIBSA
Hydrocarbyl-substituted polycarboxylic acid cornpound with a "low bismaleation
level",
especially corresponding polyisobutenylsuccinic acids or anhydrides thereof
(also referred
to overall as PIBSA) are known from the prior art. Especially advantageous are
bismaleation levels of 20% or less, or 15% or less, for example 14, 13, 12 or
10%; or 10%
or less, for example 2-9, 3-8, 4-7, 5 or 6%. The controlled preparation
thereof is described,
for example, in US 5,883,196. Suitable for preparation thereof are especially
the above
high-reactivity polyisobutenes with an Mn in the range from about 500 to 2500,
for
example 550 to 3000, 1000 to 2000 or 1000 to 1500.
A nonlimiting example of a corresponding PIBSA is Glissopal SA, derived from
HR-PIB
(Mn = 1000), with a bismaleation level of 9%.
"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.
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14
"Alkyl" or "lower alkyl" represents especially saturated, straight-chain or
branched
hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20,
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-dimethylpropyl, 1,2-
dimethylpropyl, 1-
methylpentyl, 2-methylpentyl, 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, n-octyl, n-nonyl and n-decyl,
and the singly
or multiply branched analogs thereof.
"Hydroxyalkyl" represents especially the mono- or polyhydroxylated, especially
monohydroxylated, analogs of the above alkyl radicals, for example the
monohydroxylated
analogs of the above straight-chain or branched alkyl radicals, for example
the linear
hydroxyalkyl groups with a primary hydroxyl group, such as hydroxymethyl, 2-
hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.
"Alkenyl" represents mono- or polyunsaturated, especially monounsaturated,
straight-
chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10
or 2 or to 20
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-methy1-2-propenyl, 2-methyl-2-propenyl, 1-
pentenyl, 2-
pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methy1-1-butenyl, 3-
methy1-1-
butenyl, 1-methy1-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methy1-
3-butenyl, 2-
methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethy1-2-propenyl, 1,2-dimethy1-1-
propenyl,
1,2-dimethy1-2-propenyl, 1-ethyl-1-propenyl, 1-ethy1-2-propenyl, 1-hexenyl, 2-
hexenyl, 3-
hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-
methy1-1-
pentenyl, 4-methyl-1-pentenyl, 1-methy1-2-pentenyl, 2-methyl-2-pentenyl, 3-
methy1-2-
pentenyl, 4-methyl-2-pentenyl, 1-methy1-3-pentenyl, 2-methyl-3-pentenyl, 3-
methyl-3-
pentenyl, 4-methyl-3-pentenyl, 1-methy1-4-pentenyl, 2-methyl-4-pentenyl, 3-
methy1-4-
pentenyl, 4-methyl-4-pentenyl, 1,1-dimethy1-2-butenyl, 1,1-dimethy1-3-butenyl,
1,2-
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dimethy1-1-butenyl, 1,2-dimethy1-2-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, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-
ethyl-1-
5 butenyl, 2-ethy1-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethy1-2-
propenyl, 1-ethy1-1-methy1-2-
propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
"Alkylene" represents straight-chain or mono- or polybranched hydrocarbon
bridge groups
having 1 to 10 carbon atoms, for example Cl-C7-alkylene groups selected from -
CH2-, -
10 (CH2)2-, -(CH2)3-, -CH2-CH(CH3)-, -CH (CH3)-CH2-, (CH2)4-
, -(CH2)2-CH(CH3)-,
-CH2-CH(CH3)-CH2-, (CH2)4-, -(CH2)5-, -(CH2)6, -(CH2)7-, -CH(CH3)-CH2-CH2-
CH(CH3)- or -
CH(CH3)-CH2-CH2-CH2-CH(CH3)- or C1-04-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--
15 "Alkenylene" represents the mono- or polyunsaturated, especially
monounsaturated,
analogs of the above alkylene groups having 2 to 10 carbon atoms, especially
C2-07-
alkenylenes or C2-C4-alkenylenes, 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-.
"Cyclic hydrocarbyl radicals" comprise especially:
-
cycloalkyl: 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 to cyclopropylmethyl, cyclopropylethyl,
cyclobutylmethyl,
cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or C3-
C7-cycloalkyl
such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclopropylmethyl,
cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl, cyclohexylmethyl, where
the bond to
the rest of the molecule may be via any suitable carbon atom.
CA 02840524 2013-12-27
16
cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having 5 to 8,
preferably up to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-
3-yl,
cyclohexen-1-yl, cyclohexen-3-y1 and cyclohexen-4-y1;
aryl: 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, -COON, -COO-alkyl, ¨OH, -SH, -ON, amino, -NO2,
alkyl, or
alkenyl groups.
The term "about" in the context of a stated figure or of a value range denotes
deviations
from the specifically disclosed values. These are usually customary
deviations. These may
differ, for example, by 10% to 0.1% from the specific values. Typically,
such deviations
are about 8% to 1% or 5%, 4%, 3% or 2%.
A3) Polycarboxylic acid compounds and hydrocarbyl-substituted polycarboxylic
acid
compounds:
The polycarboxylic acid compounds used are aliphatic di- or polybasic (for
example tri- or
tetrabasic), especially from di-, tri- or tetracarboxylic acids and analogs
thereof, such as
anhydrides or lower alkyl esters (partially or completely esterified), and is
optionally
substituted by one or more (for example 2 or 3), especially a long-chain alkyl
radical and/or
a high molecular weight hydrocarbyl radical, especially a polyalkylene
radical. Examples
are C3¨Cl0 polycarboxylic acids, such as the dicarboxylic acids malonic acid,
succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and
sebacic acid, and the
branched analogs thereof; and the tricarboxylic acid citric acid; and
anhydrides or lower
alkyl esters thereof of. The polycarboxylic acid compounds can also be
obtained from the
corresponding monounsaturated acids and addition of at least one long-chain
alkyl radical
CA 02840524 2013-12-27
17
and/or high molecular weight hydrocarbyl radical. Examples of suitable
monounsaturated
acids are fumaric acid, maleic acid, itaconic acid.
The hydrophobic "long-chain" or "high molecular weight" hydrocarbyl radical
which
ensures sufficient solubility of the quaternized product in the fuel has a
number-average
molecular weight (Mr) 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.
Typical
hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and
polyisobutenyl
radicals, for example with a number-average molecular weight Mr of 3500 to
5000, 350 to
.. 3000, 500 to 2500, 700 to 2500 and 800 to 1500.
Suitable hydrocarbyl-substituted compounds are described, for example, in DE
43 19 672
and WO 2008/138836.
Suitable hydrocarbyl-substituted polycarboxylic acid compounds also comprise
polymeric,
especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid
compounds.
Dimeric forms comprise, for example, two acid anhydride groups which can be
reacted
independently with the quaternizable nitrogen compound in the preparation
process
according to the invention.
A4) Quaternizing agents:
Useful quaternizing agents are in principle all alkyl esters which are
suitable as such and
are those 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).
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
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18
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, and R100C(0)-, in which
Ria is as
defined above for R1 and R3 is H or Ri;
and
b) compounds of the general formula 2
OC(0)-A-C(0)0Ria (2)
in which
R1 and Ria are each independently a lower alkyl radical and
A is hydrocarbylene (such as alkylene or alkenylene).
Particularly suitable compounds of the formula 1 are those in which
R1 is a 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 pare, 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.
A5) Quatemized or quaternizable nitrogen compounds:
CA 02840524 2013-12-27
19
The quaternizable nitrogen compounds reactive with the polycarboxylic acid
compound
are selected from
a. hydroxyalkyl-substituted mono- or polyamines having at least one
quaternized (e.g. choline) or quaternizable primary, secondary or tertiary
amino
group;
b. straight-chain or branched, cyclic, heterocyclic, aromatic or
nonaromatic
polyamines having at least one primary or secondary (anhydride-reactive) amino
group and having at least one quaternized or quaternizable primary, secondary
or
tertiary amino group;
c. piperazines.
The quaternizable nitrogen compound is especially selected from
d. hydroxyalkyl-substituted primary, secondary, tertiary or quaternary
monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or
quaternary
diamines;
e. straight-chain or branched aliphatic diamines having two primary amino
groups; di- or polyamines having at least one primary and at least one
secondary
amino group; di- or polyamines having at least one primary and at least one
tertiary
amino group; di- or polyamines having at least one primary and at least one
quaternary amino group; aromatic carbocyclic diamines having two primary amino
groups; aromatic heterocyclic polyamines having two primary amino groups;
aromatic
or nonaromatic heterocycles having one primary and one tertiary amino group.
Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those
provided
with at least one hydroxyalkyl substituted, for example 1, 2, 3, 4, 5 or 6
hydroxyalkyl
substituted.
Examples of "hydroxyalkyl-substituted monoamines" include: N-hydroxyalkyl
monoamines,
N,N-dihydroxyalkyl monoamines and N,N,N-trihydroxyalkyl monoamines, where the
hydroxyalkyl groups are the same or different and are also as defined above.
Hydroxyalkyl
is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
CA 02840524 2013-12-27
For example, the following "hydroxyalkyl-substituted polyamines" and
especially
"hydroxyalkyl-substituted diamines" may be mentioned: (N-
hydroxyalkyl)alkylenediamines,
N,N-dihydroxyalkylalkylenediamines, where the hydroxyalkyl groups are the same
or
5 different and are also as defined above. Hydroxyalkyl is especially 2-
hydroxyethyl, 3-
hydroxypropyl or 4-hydroxybutyl; alkylene is especially ethylene, propylene or
butylene.
Suitable "diamines" are alkylenediamines, and the N-alkyl-substituted analogs
thereof,
such as N-monoalkylated alkylenediamines and the N,N- or N,N'-dialkylated
10 alkylenediamines, Alkylene is especially straight-chain or branched C1-7-
or Cl_a_alkylene as
defined above. Alkyl is especially 01-4-alkyl as defined above. Examples are
especially
ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-
butylenediamine and
isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers
thereof, heptanediamine and isomers thereof, and singly or multiply, for
example singly or
15 doubly, Ci-C4-alkylated, for example methylated, derivatives of the
aforementioned
diamine compounds such as 3-dimethylamino-1-propylamine (DMAPA), N,N-
diethylaminopropylamine and N,N-dimethylaminoethylamine.
Suitable straight-chain "polyamines" are, for example, dialkylenetriamine,
20 trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and
the N-alkyl-
substituted analogs thereof, such as N-monoalkylated and the N,N- or N,N'-
dialkylated
alkylenepolyamines. Alkylene is especially straight-chain or branched C1_7-.
or Ci_a_alkylene
as defined above. Alkyl is especially C1.4-alkyl as defined above.
Examples are especially diethylenetriamine, triethylenetetramine,
tetraethylenepentamine,
pentaethylenehexamine, dipropylenetriamine,
tripropylenetetramine,
tetrapropylenepentamine, pentapropylenehexamine,
dibutylenetriamine,
tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine; and the
N,N-dialkyl
derivatives thereof, especially the N,N-di-C1.4-alkyl derivatives thereof.
Examples include:
N,N-dimethyldimethylenetriamine, N,N-diethyldimethylenetriamine, N, N-
dipropyldimethylenetriamine, N,N-dimethyldiethylene-1,2-triamine, N,N-
diethyldiethylene-
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21
1,2-triamine, N,N-dipropyldiethylene-1,2-triamine, N,N-dimethyldipropylene-1,3-
triamine
(i.e. DMAPAPA), N,N-diethyldipropylene-1,3-triamine, N,N-dipropyldipropylene-
1,3-
triamine, N,N-dimethyldibutylene-1,4-triamine, N,N-diethyldibutylene-1,4-
triamine, N,N-
dipropyldibutylene-1,4-triamine, N,N-dimethyldipentylene-1,5-triamine,
N,N-
diethyldipentylene-1,5-triamine, N,N-dipropyldipentylene-1,5-triamine,
N,N-
dimethyldihexylene-1,6-triamine, N,N-diethyldihexylene-1,6-triamine and
N,N-
dipropyldihexylene-1,6-triamine.
"Aromatic carbocyclic diamines" having two primary amino groups are the
diamino-
substituted derivatives of benzene, biphenyl, naphthalene,
tetrahydronaphthalene,
fluorene, indene and phenanthrene.
"Aromatic or nonaromatic heterocyclic polyamines" having two primary amino
groups are
the derivatives, substituted by two amino groups, of the following
heterocycles:
5- or 6-membered, saturated or monounsaturated heterocycles comprising one to
two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen
and/or sulfur
atoms as ring members, for example tetrahydrofuran, pyrrolidine,
isoxazolidine,
isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine,
pyrroline, piperidine,
piperidinyl,
tetrahydropyran, hexahydropyridazine, hexahydropyrimidine,
piperazine;
5-membered aromatic heterocycles comprising, in addition to carbon atoms, two
or
three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen
atom as ring
members, for example furan, thiane, pyrrole, pyrazole, oxazole, thiazole,
imidazole and
1,3,4-triazole; isoxazole, isothiazole, thiadiazole, oxadiazole;
6-membered heterocycles comprising, in addition to carbon atoms, one or two,
or
one, two or three, nitrogen atoms as ring members, for example pyridinyl,
pyridazine,
pyrimidine, pyrazinyl, 1,2,4-triazine, 1,3,5-triazin-2-yl.
CA 02840524 2013-12-27
22
"Aromatic or nonaromatic heterocycles having one primary and one tertiary
amino group"
are, for example, the abovementioned N-heterocycles which are aminoalkylated
on at
least one ring nitrogen atom, and especially bear an amino-C1.4--alkyl group.
"Aromatic or nonaromatic heterocycles having a tertiary amino group and a
hydroxyalkyl
group" are, for example, the abovementioned N-heterocycles which are
hydroxyalkylated
on at least one ring nitrogen atom, and especially bear a hydroxy-C1.4-alkyl
group.
Mention should be made especially of the following groups of individual
classes of
.. quaternizable nitrogen compounds:
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23
Group 1:
NAME FORMULA
Diamines with primary second nitrogen atom
Ethylenediamine H2 NH2
NH 2
1,2-Propylenediamine H2
1,3-Propylenediamine H2
HN NH
Isomeric butylenediamines, for example
1,5-Pentylenediamine FI2N-NH2
H 2
NH2
Isomeric pentanediamines, for example
H2 N
2
Isomeric hexanediamines, for example
Isomeric heptanediamines, for example H2 NH2
Di- and polyamines with a secondary second nitrogen atom
H2
Diethylenetriamine (DETA)
Dipropylenetriamine (DPTA), 3,3"-iminobis(N,N H NH
-
dimethylpropylamine)
Triethylenetetramine (TETA)
NH2
H 2 H2
Tetraethylenepentamine (TEPA) N
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24
H21\1"
NH2 HN
Pentaethylenehexamine
N-Methyl-3-amino-1-propylamine N N H 2
H
NH2
Bishexamethylenetriamine
NH2
Aromatics
H2N
Diaminobenzenes, for example
H2N
H2N,
Diaminopyridines, for example
H2NN
Group 2:
NAME FORMULA
Heterocycles
H N
2
1-(3-Aminopropyl)imidazole LIN
4-(3-Aminopropyl)morpholine
H2
\N NH2
1-(2-Aminoethylpiperidine)
N/ \N NH2
2-(1-Piperazinyl)ethylamine (AEP)
CA 02840524 2013-12-27
/ \
N-Methylpiperazine N¨
\ /
Amines with a tertiary second nitrogen atom
3,3-Diamino-N-methyldipropylamine
NH2
H2Ne
3-Dimethylamino-1-propylamine (DMAPA)
N,N-Diethylaminopropylamine H2N
NN-Dimethylaminoethylamine
Group 3:
NAME FORMULA
Alcohols with a primary and secondary amine
Ethanolamine H2NOH
3-Hydroxy-1-propylamine H2N OH
HON
Diethanolamine
N,OH
HON
Diisopropanolamine
CA 02840524 2013-12-27
26
N-(2-Hydroxyethyl)ethylenediamine ,
NH2
HO
Alcohols with a tertiary amine
OH
Triethanolamine, (2,21,21I-Nitrilotriethanol)
OH
1-(3-Hydroxypropyl)imidazole
HO /---OH
Tris(hydroxymethyl)amine \--N
\--OH
3-Dimethylamino-1-propanol OH
3-Diethylamino-1-propanol HO
2-Dimethylamino-1-ethanol
4-Diethylamino-1-butanol
A6) Preparation of inventive additives:
CA 02840524 2013-12-27
27
a) Reaction with oxygen or nitrogen group
The hydrocarbyl-substituted polycarboxylic acid compound can be reacted with
the
quaternizable nitrogen compound according to the present invention under
thermally
controlled conditions, such that there is essentially no condensation
reaction. More
particularly, no formation of water of reaction is observed in that case. More
particularly,
such a reaction is effected at a temperature in the range from 10 to 80 C,
especially 20 to
60 C or 30 to 50 C. The reaction time may be in the range from a few minutes
or a few
hours, for example about 1 minute up to about 10 hours. The reaction can be
effected at a
pressure of about 0.1 to 2 atm, but especially at approximately standard
pressure. For
example, an inert gas atmosphere, for example nitrogen, is appropriate.
More particularly, the reaction can also be effected at elevated temperatures
which
promote condensation, for example in the range from 90 to 100 C or 100 to 170
C. The
reaction time may be in the region of a few minutes or a few hours, for
example about
1 minute up to about 10 hours. The reaction can be effected at pressure at
about 0.1 to
2 atm, but especially at about standard pressure.
The reactants are initially charged especially in about equimolar amounts;
optionally, a
small molar excess of the polycarboxylic acid compound, for example a 0.05- to
0.5-fold,
for example a 0.1- to 0.3-fold, excess, is desirable. If required, the
reactants can be initially
charged 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. The
solvent can also serve, for example, to remove water of condensation
azeotropically from
the reaction mixture. More particularly, however, the reactions are performed
without
solvent.
The reaction product thus formed can theoretically be purified further, or the
solvent can
be removed. Usually, however, this is not absolutely necessary, such that the
reaction step
CA 02840524 2013-12-27
28
can be transferred without further purification into the next synthesis step,
the
quaternization.
b) Quaternization
The quaternization in reaction step (b) is then carried out in a manner known
per se.
To perform the quaternization, the reaction product or reaction mixture from
stage a) 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 2.0, 0.2 to 1.5 or 0.5 to 1.25 equivalents, of
quaternizing agent per
equivalent of quatemizable tertiary nitrogen atom. More particularly, however,
approximately equimolar proportions of the compound are used to quaternize a
tertiary
amine group. Correspondingly higher use amounts are required to quaternize a
secondary
or primary amine group. In a further/ variant, the quaternizing agent is added
in excess, for
example 1.1 to 2.0, 1.25 to 2 or 1.25 to 1.75 equivalents of quaternizing
agent per
equivalent of quaternizable tertiary nitrogen atom.
Typical working temperatures here are in the range from 50 to 180 C, for
example from 90
to 160 C or 100 to 140 C. The reaction time may be in the range 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, or a sufficient
proportion of
solvent from reaction step a) is still present. Typical examples are, for
example, solvents of
the Solvesso series, toluene or xylene. 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 CI-Cis-
CA 02840524 2013-12-27
29
monocarboxylic acids such as especially lauric acid, isononanoic acid or
neodecanoic
acid. 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.
c) Workup of the reaction mixture
The reaction end product thus formed can theoretically be purified further, or
the solvent
can be removed. In order to improve the further processability of the
products, however, it
is also possible to add solvent after the reaction, for example solvents from
the Solvesso
series, 2-ethylhexanol, or essentially aliphatic solvents. Usually, however,
this is not
absolutely necessary, and so the reaction product is usable 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, 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:
CA 02840524 2013-12-27
B1) Detergent additives
The customary detergent additives are preferably amphiphilic substances which
possess
5 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 their alkali metal or alkaline earth metal salts;
(De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(Df) 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 Mann ich reaction of substituted phenols with
aldehydes and
mono- or polyamines.
CA 02840524 2013-12-27
31
The hydrophobic hydrocarbon radical in the above detergent additives, which
ensures the
adequate solubility in the fuel, has a number-average molecular weight (Ma) 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 Ma 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 M = 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 7 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 in
particular in
WO-A 94/24231.
CA 02840524 2013-12-27
32
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 in particular in WO-A 97/03946.
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 in particular 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 in particular in WO-A 96/03367 and in WO-A
96/03479.
These reaction products are generally mixtures of pure nitropolyisobutenes
(e.g. a,13-
dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. a-nitro-r3-
hydroxypolyisobutene).
Additives comprising hydroxyl groups in combination with mono- or polyamino
groups (Dc)
are in particular 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 in particular 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 in
particular 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.
CA 02840524 2013-12-27
33
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 in particular 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
C30-
alkanediols, mono- or di-C2- to C30-alkylamines, C1- to C30-alkylcyclohexanols
or Cl- 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 in particular 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 of these are tridecanol butoxylates, isotridecanol
butoxylates,
isononylphenol butoxylates and 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, in particular those
having a
minimum viscosity of 2 mm2/s at 100 C, as described in particular 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 have 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
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34
corresponding derivatives of polyisobutenylsuccinic anhydride which are
obtainable by
reacting conventional or high-reactivity polyisobutene having M = 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 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 stem from
conventional or high-reactivity polyisobutene having Mn = 300 to 5000. Such
"polyisobutene Mannich bases" are described in particular in EP-A 831 141.
CA 02840524 2013-12-27
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.
5 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 to 2000 class; but also
aromatic
10 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 from about 360 to 500 C, obtainable from
natural
mineral oil which has been catalytically hydrogenated and isomerized under
high pressure
and also deparaffinized). Likewise suitable are mixtures of the abovementioned
mineral
15 carrier oils.
Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins
or
polyinternalolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic
polyether-amines,
alkyl phenol-started polyethers, alkylphenol-started polyetheramines and
carboxylic esters
20 of long-chain alkanols.
Examples of suitable polyolefins are olefin polymers having Mn = 400 to 1800,
in particular
based on polybutene or polyisobutene (hydrogenated or unhydrogenated).
25 Examples of suitable polyethers or polyetheramines are preferably
compounds comprising
polyoxy-C2- to Ca-alkylene moieties which are obtainable by reacting C2- to
C60-alkanols,
C6- to C30-alkanediols, mono- or di-C2- to C30-alkylamines, Cl- to C30-
alkylcyclohexanols or
C1- 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
30 polyetheramines, by subsequent reductive amination with ammonia,
monoamines or
polyamines. Such products are described in particular in
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36
EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, the
polyetheramines used may be poly-02- 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 in particular esters
of mono-, di-
or tricarboxylic acids with long-chain alkanols or polyols, as described in
particular in DE-A
38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or
aromatic acids;
suitable ester alcohols or polyols are in particular 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 42 241, DE-A 43 09 074, EP-A 452 328 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
03- to C6-alkylene oxide units, for example selected from 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 in particular a
straight-chain or
branched 06- to 018-alkyl radical. Particular examples include tridecanol and
nonylphenol.
Particularly preferred alcohol-started polyethers are the reaction products
(polyetherification products) of monohydric aliphatic 06- to G18-alcohols with
03- to
06-alkylene oxides. Examples of monohydric aliphatic 06-018-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
CA 02840524 2013-12-27
37
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
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. In particular,
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, though, also possible to use mixtures of organic compounds
effective as
MDFIs and/or effective as WASAs and/or effective as nucleators.
CA 02840524 2013-12-27
38
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 Ito 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, more preferably 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 Cm-olefin base monomer. When, for
example, the
olefin base monomer used is ethylene or propene, suitable further olefins are
in particular
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 Cl- to 020-
alkanols, especially Ci- to C10-alkanols, in particular with methanol,
ethanol, propanol,
CA 02840524 2013-12-27
39
isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol,
hexanol, heptanol,
octanol, 2-ethylhexanol, nonanol and decanol, and structural isomers thereof.
Suitable alkenyl carboxylates are, for example, 02- to C14-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, the
a-carbon
atom more preferably being tertiary, i.e. the carboxylic acid being a so-
called
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 their preparation 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 02- to C40-a-olefin, a to
C20-alkyl ester of an ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a 02- to 014-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. A
CA 02840524 2013-12-27
typical 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
5 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.
10 The copolymers of class (K1) preferably have a number-average molecular
weight Mn of
1000 to 20000, more preferably 1000 to 10 000 and in particular 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
15 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
20 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.
Sc!.
Macromolecular Revs. 8, pages 117 to 253 (1974)'. Mixtures of comb polymers
are also
25 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,
30 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
CA 02840524 2013-12-27
41
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, in particular at least
two
substituents, in the form of a tertiary nitrogen atom of the general formula
>NR7 in which
R7 is a C8- to 040-hydrocarbon 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 derivative thereof. The amines preferably comprise at least one
linear 08- to 040-
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, in particular 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.
In particular, the component of class (K4) is an oil-soluble reaction product
of poly(02- to
020-carboxylic acids) having at least one tertiary amino group with primary or
secondary
amines. The poly(02- 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
CA 02840524 2013-12-27
42
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 029-carboxylic acids) which have at least one tertiary amino group
and are of
the general formula Ila or Ilb
HOOC,B B-COOH
HOOC,B,N,A.N.B.COOH
(11a)
HOOC NB COOH
B,COOH (11b)
in which the variable A is a straight-chain or branched C2- to Cs-alkylene
group or the
moiety of the formula III
HOOCB CH2-CH2-
õN-
CH2-CH2-
(Ill)
and the variable B is a to C19-alkylene group. The compounds of the general
formulae
Ila and Ilb especially have the properties of a WASA.
Moreover, the preferred oil-soluble reaction product of component (K4),
especially that of
the general formula Ila or I lb, 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.
CA 02840524 2013-12-27
43
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 in particular 1,2-ethylene. The variable A
comprises
preferably 2 to 4 and especially 2 or 3 carbon atoms.
01- to 019-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 010- to 030-alkyl radicals,
especially Cu- to
024-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
relatively long-chain alkyl radicals, derive from naturally occurring fatty
acid and from
derivatives thereof. The two R8 radicals are preferably identical.
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.
CA 02840524 2013-12-27
44
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, dipalmitinamine, dicoconut fatty amine, distearylamine,
dibehenylamine or
especially ditallow fatty amine. A particularly preferred component (K4) is
the reaction
product of 1 mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated
ditallow
fatty amine.
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 ditallow fatty amine, the latter being hydrogenated or
unhydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone
with 2 mol
of a dialkylamine, for example ditallow fatty amine and/or tallow fatty amine,
the last 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 which are
suitable as cold flow
improvers 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 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 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 014 and Cis alcohols, the acid groups having
been
45
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 improvers.
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 TM (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
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46
propylene oxide (PO), for example including in the form of BO/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 7D07Tm (Nalco) and
TOLAD 2683TM (Petrolite).
B8) Antifoams
Suitable antifoams are, for example, polyether-modified polysiloxanes, for
example the
products available under the trade names TEGOPREN 5851 TM (Goldschmidt), Q
25907Tm
(Dow Corning) and RHODOSILTM (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.
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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 SHELLSOLTM (Royal Dutch/Shell Group) and EXXSOLTM
(ExxonMobil),
and also polar organic solvents, for example, alcohols such as 2-ethylhexanol,
decanol
and isotridecanol. 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
so-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
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48
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.).
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
CA 02840524 2013-12-27
49
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.
The invention is now illustrated in detail by the working examples which
follow. The test
methods described herein are not restricted to the specific working examples,
but are part
of the general disclosure of the description and can be employed generally in
the context
of the present invention.
Experimental section:
A. General test methods
Engine test
bl) XUD9 test ¨ determination of flow restriction
The procedure was according to the standard stipulations of GEC F-23-01.
b2) DW10 ¨ keep clean test
To examine the influence of the inventive compounds on the performance of
direct-
injection diesel engines, the power loss was determined on the basis of the
official test
method CEC F-098-08. The power loss is a direct measure of formation of
deposits in the
injectors.
50
The keep clean test is based on CEC test procedure F-098-08 Issue 5. The same
test
setup and engine type (PEUGEOT Tm DW10) as in the CEC procedure are used.
Special features of the test used:
a) Injectors
in the tests, cleaned injectors were used. The cleaning time in an ultrasound
bath in water
at 60 C + 10% Superdecontamine (Intersciences, Brussels) was 4 h.
b) Test run times
the test period was 12 h without shutdown phases. The one-hour test cycle (see
table
below) from CEC F-098-08 was run through 12 times.
Stage Duration Engine speed Load Torque Charge air
(minutes) (rpm) (%) (Nm) temperature
+1- 20 +1- 5 downstream of
charge run cooler
( C) +1- 3
1 2 1750 (20) 62 45
2 7 3000 (60) 173 50
3 2 1750 (20) 62 45
4 7 3500 (80) 212 50
5 2 1750 (20) 62 45
6 10 4000 100 * 50
7 2 1250 (10) 25 43**
8 7 3000 100 * 50
9 2 1250 (10) 25 43**
10 10 2000 100 * 50
11 2 1250 (10) 25 43**
12 7 4000 100 * 50
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51
1=1 h
* for range to be expected see CEC-098-08
** target value
c) Power 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 warmed up. The
procedure
is described in Issue 5 of the test procedure CEC F-98-08. The same test setup
and the
PEUGEOTTm DW10 engine type are used.
The final power (Pend, KC) is determined in the 12th cycle in stage 12, (see
table above).
Here too, the operating point is full load 4000/min. P
= end, KC [kW] is calculated from the
measured torque.
The power loss in KC is calculated as follows:
power loss, KC [c70] = (1
- = P end,KC / Po,KC) x 100
The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To
synthetically
induce the formation of deposits at the injectors, 1 ppm of zinc was added
thereto in the
form of a zinc neodecanoate solution.
B. Preparation examples:
Reactants used:
PIBSA: Prepared from maleic anhydride and PIB 1000 in a known manner. For the
inventive preparation examples and comparative examples which follow,
qualities with
hydrolysis numbers in the region of 84-95 mg KOH/g were used. DMAPA was used
with
the particular PIBSA quality in a molar ratio of 1:1 according to the
hydrolysis number. The
PIBSA qualities used had bismaleation levels (BML) of less than 15%.
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52
DMAPA: M = 102.18
methyl salicylate: M = 152.14
dimethyl phthalate: M = 194.19
dimethyl oxalate: M = 118.09
dimethyl sulfate: M = 126.13
dimethyl carbonate M = 90.08
Preparation example 1: Synthesis of an inventive quaternized succinimide
(PIBSA/DMAPA/dimethyl phthalate)
Polyisobutylenesuccinic anhydride (1659 g) is dissolved in Solvent Naphtha
Heavy (SNH,
Exxon moo CAS64742-95-5) (1220 g), and 3-dimethylamino-1-propylamine (DMAPA;
153 g) is added. The reaction solution is stirred at 170 C for 8 h, in the
course of which
water of condensation formed is distilled off continuously. This affords the
PIBSA-DMAPA
succinimide as a solution in Solvent Naphtha Heavy (TBN 0.557 mmol/g).
A portion of this solution of the PIBSA-DMAPA succinimide (181 g) is added to
dimethyl
phthalate (19.4 g), and the resulting reaction solution is stirred at 120 C
for 11 hand then
at 150 C for 24 h. After cooling to room temperature, the product obtained is
the
ammonium carboxylate as a solution in Solvent Naphtha Heavy. 'H NMR analysis
confirms the quaternization.
Preparation example 2: Synthesis of an inventive quaternized succinimide
(PIBSA/DMAPA/methyl salicylate)
Polyisobutylenesuccinic anhydride (PIBSA; 2198 g) is heated to 110 C, and 3-
dimethyl-
amino-1-propylamine (DMAPA; 182 g) is added within 40 min, in the course of
which the
reaction mixture heats up to 140 C. The reaction mixture is heated to 170 C
and held at
this temperature for 3 h, in the course of which 28 g of distillate are
collected. This affords
the PIBSA-DMAPA succinimide as a viscous oil (TBN 0.735 mmol/g).
=
53
A mixture of this PIBSA-DMAPA succinimide (284.5 g), methyl salicylate (65.5
g) (i.e.
about 2 equivalents of methyl salicylate per equivalent of tertiary amino
group) and 3,3,5-
trimethylheptanoic acid (from BASF) (0.75 g) is heated to 140-150 and the
reaction
mixture is stirred at this temperature for 6 h. After cooling to room
temperature, the product
obtained is the ammonium salicylate as a viscous oil. 1H NMR analysis confirms
the
quaternization. By adding Pilot 900TM oil, Petrochem Carless Ltd., the active
ingredient
content of the solution is adjusted to 50% by weight.
Preparation example 3: Synthesis of an inventive quaternized succinimide
(PIBSA/DMAPA/dimethyl oxalate)
Polyisobutylenesuccinic anhydride (PIBSA; 2198 g) is heated to 110 C, and 3-
dimethyl-
amino-1-propylamine (DMAPA; 182 g) is added within 40 min, in the course of
which the
.. reaction mixture heats up to 140 C. The reaction mixture is heated to 170 C
and held at
this temperature for 3 h, in the course of which 28 g of distillate are
collected. This affords
the PIBSA-DMAPA succinimide as a viscous oil (TBN 0.735 mmol/g).
A mixture of this PIBSA-DMAPA succinimide (211 g), dimethyl oxalate (34.5 g)
and lauric
acid (4.9 g) is heated to 120 C and then stirred at this temperature for 4 h.
Excess
dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p =
5 mbar)
at 120 C. The product obtained is the ammonium methyl oxalate as a viscous
oil. 1H NMR
analysis confirms the quaternization.
For comparison with the prior art, Examples 2 and 4 from WO 2006/135881 were
worked
up.
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54
Preparation example 4: Synthesis of a known quaternized succinimide
(comparative
example) (Example 2 from WO 2006/135881)
A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Carless Ltd., (51.3
g) is initially
charged and heated to 110 C. DMAPA (31.4g) is metered in within 50 minutes, in
the
course of which a slightly exothermic reaction is observed. Within 80 minutes,
the reaction
mixture is heated to 150 C and the mixture is then kept at this temperature
for 3 h, in the
course of which the water of reaction which forms is distilled off. After
cooling to room
temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot
900 oil (TBN
0.62 mmol/g).
A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot
900 oil,
Petrochem Carless Ltd., (354 g) is initially charged and heated to 90 C.
Dimethyl sulfate
(26.3 g) is metered in, in the course of which the reaction temperature rises
to 112 C.
Subsequently, the reaction mixture is stirred at 100 C for 3 h. After cooling
to room
temperature, the quaternized PIBSA-DMAPA succinimide is obtained as a solution
in Pilot
900 oil. 1H NMR confirmed the quaternization. The output was adjusted to an
active
ingredient content of 50% by weight by adding Pilot 900 oil.
Preparation example 5: Synthesis of a known quaternized succinimide
(comparative
example) (Example 4 from WO 2006/135881)
A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Carless Ltd., (51.3
g) is initially
charged and heated to 110 C. DMAPA (31.4 g) is metered in within 50 minutes,
in the
course of which a slightly exothermic reaction is observed. Within 80 minutes,
the reaction
mixture is heated to 150 C and the mixture is then kept at this temperature
for 3 h, in the
course of which the water of reaction which forms is distilled off. After
cooling to room
temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot
900 oil (TBN
0.62 mmol/g).
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A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot
900 oil,
Petrochem Carless Ltd., (130 g), dimethyl carbonate (20 g) and methanol (17.4)
are
charged into an autoclave and inertized with nitrogen, and a starting pressure
of 1.3 bar is
established. Subsequently, the reaction mixture is stirred under autogenous
pressure first
5 at 90 C for 1 h, then at 140 C for 24 h. After cooling to room
temperature, the autoclave is
decompressed and the contents are rinsed out completely with a little toluene
as a solvent.
All low-boiling constituents are subsequently removed on a rotary evaporator
under
reduced pressure to obtain the quaternized PIBSA-DMAPA succinimide as a
solution in
Pilot 900 oil. 1H NMR analysis confirmed the partial quaternization. The
output is adjusted
10 to an active ingredient content of 50% by weight by adding Pilot 900
oil.
C. Use examples:
In the use examples which follow, the additives are used either as a pure
substance (as
15 synthesized in the above preparation examples) or in the form of an
additive package.
Ml: Additive according to preparation example 2 (inventive, quaternized with
methyl
salicylate)
M2: Additive according to preparation example 4 (comparative, quaternized with
dimethyl
20 sulfate)
M3: Additive according to preparation example 5 (comparative, quaternized with
dimethyl
carbonate)
Use example 1: determination of the additive action on the formation of
deposits in diesel
25 engine injection nozzles
a) XUD9 Tests
Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The results are compiled in table 1:
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56
Table 1: XUD9 tests
Ex. Name Dosage according to Flow restriction
preparation example 0.1 mm needle
[mg/kg] stroke ['A]
#1 Ml, according to 30 10.7
preparation example 2
#2 M2, according to 30 48.5
preparation example 4
#3 M3, according to 30 20.8
preparation example 5
It was found that the inventive additive Ml, with the same dosage, has an
improved effect
compared to the prior art (M2, M3).
b) DW10 test
To study the influence of the inventive compound on the performance of direct-
injection
diesel engines, the power loss was determined based on the official test
method CEC
F-098-08 as described above. The power loss is a direct measure of formation
of deposits
in the injectors. A conventional direct-injection diesel engine with a common-
rail system
was used.
The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To
synthetically
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.
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 P = end the power at the end of the
measurement:
The test results are shown in table 2.
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57
Table 2: Results of the DW10 test
Dose Time Po Pen
- d
Additive Power loss
[mg/kg] [h] [KW] [KW]
Base value 0 12 99.3 94.3 5.0%
Ml, according to preparation
160 12 98.7 97.4 1.32%
example 2
M2, according to preparation
160 12 99 98.1 0.9%
example 4
M3, according to preparation
160 12 98.1 95.7 2.4%
example 5
It was found that the inventive additive M1 has an improved effect compared to
the base
value and has an improved effect at least compared to example M3.
Use example 2: Determination of the solubility properties
To determine the solubility properties, the following additive packages were
produced and
tested:
M 4 (inventive)
Substance Content [ppm]
Additive acc. to preparation example 2 160.00
Dehazer, commercial 3.00
Antifoam, silicone-based, commercial 6.00
Solvent Naphtha Heavy 80.00
Total 249.00
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M 5 (comparative, dimethyl sulfate)
Substance Content [ppm]
Additive acc. to preparation example 4 160.00
Dehazer, commercial 3.00
Antifoam, silicone-based, commercial 6.00
Solvent Naphtha Heavy 420.00
Total 589.00
M 6 (comparative, dimethyl carbonate)
Substance Content [ppm]
Additive acc. to preparation example 5 160.00
Dehazer (commercial) 3.00
Antifoam, silicone-based, commercial 6.00
Solvent Naphtha Heavy 150.00
Total 319.00
The result of the solubility tests is compiled in the table below. The minimum
amount of
solvent (Solvent Naphtha Heavy) needed to obtain a homogeneous, clear diesel
performance package at room temperature with otherwise identical amounts of
active
substance, Pilot 900, antifoam and dehazer is reported.
.. Table 3: Determination of the solvent requirement
Additive Additive Minimum amount of
solvent needed for a
package
homogeneous package
PIBSA-DMAPA-imide-methyl salicylate M4 32%
PIBSA-DMAPA-imide-dimethyl sulfate M5 71%
PIBSA-DMAPA-imide-dimethyl carbonate M6 47%
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59
It was found that, surprisingly, the additive according to preparation example
2 has the
best solubility properties, i.e. requires the least solvent.
Reference is made explicitly to the disclosure of the publications cited
herein.
