Note: Descriptions are shown in the official language in which they were submitted.
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Quaternized polyetheramines and use thereof as additives in fuels and
lubricants
The present invention relates to novel quaternized polyetheramines and to the
preparation
thereof. The present invention further relates to the use of these compounds
as a fuel and
lubricant additive. More particularly, the invention 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. The
invention also
provides additive packages comprising these polyetheramines; and fuels and
lubricants
additized therewith. The invention further relates to the use of these
quaternized nitrogen
compounds as an additive for gasoline fuels, especially for improving the
intake system
cleanliness of gasoline engines.
State of the art:
In direct injection diesel engines, the fuel is injected and distributed
ultrafinely (nebulized) by
a multihole injection nozzle which reaches directly into the combustion
chamber in 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.
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In the common rail system, the diesel fuel is conveyed by a pump with
pressures up to
2000 bar into a high-pressure line, the common rail. Proceeding from the
common rail,
branch lines run to the different injectors which inject the fuel directly
into the combustion
chamber. The full pressure is always applied to the common rail, which enables
multiple
.. injection or a specific injection form. In the other injection systems, in
contrast, only smaller
variation in the injection is possible. The injection in the common rail is
divided essentially
into three groups: (1.) pre-injection, by which essentially softer combustion
is achieved, such
that harsh combustion noises ("nailing") are reduced and the engine seems to
run quietly;
(2.) main injection, which is responsible especially for a good torque
profile; and (3.) post-
injection, which especially ensures a low NO value. In this post-injection,
the fuel is generally
not 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 NOR.
The variable, cylinder-individual injection in the common rail injection
system can positively
influence the pollutant emission of the engine, for example the emission of
nitrogen oxides
(NOR), carbon monoxide (CO) and especially of particulates (soot). This makes
it possible, for
example, for engines equipped with common rail injection systems 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.
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Carburetors and intake systems of gasoline engines, but also injectors of
injection systems
for fuel dosage, are contaminated by impurities which are caused by dust
particles from the
air, uncombusted hydrocarbon residues from the combustion chamber and the
crankcase
ventilation gases passed into the carburetor.
These residues shift the air-fuel ratio when idling and in the lower partial
load range, such
that the mixture becomes leaner, the combustion becomes less complete and, in
turn, the
proportions of uncombusted or partly combusted hydrocarbons in the exhaust gas
become
greater and the gasoline consumption rises.
It is known that these disadvantages are avoided by using fuel additives to
maintain
cleanliness of valves and carburetors or injection systems of gasoline engines
(cf., for
example: M. Rossenbeck in Katalysatoren, Tenside, Mineraloladditive
[Catalysts,
Surfactants, Mineral Oil Additives], eds. J. Falbe, U. Hasserodt, p. 223, G.
Thieme Verlag,
Stuttgart 1978).
According to the mode of action, but also the preferred site of use of such
detergent
additives, a distinction is now drawn between two generations.
The first additive generation could merely prevent the formation of deposits
in the intake
system, but not remove deposits already present, whereas the modern second
generation
additives can do both (keep-clean and clean-up effect), more particularly also
due to their
outstanding thermal stability in zones of relatively high temperatures, namely
at the intake
valves. Such detergents, which can come from a multitude of chemical substance
classes,
for example polyalkeneamines, polyetheramines, polybutene Mannich bases or
polybutenesuccinimides, are generally employed in combination with carrier
oils and in some
cases further additive components, for example corrosion inhibitors and
demulsifiers. The
carrier oils exert a solvent or wash function in combination with the
detergents. Carrier oils
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are generally high-boiling, viscous, thermally stable liquids which coat the
hot metal surface
and thus prevent the formation or deposition of impurities on the metal
surface.
Recent generations of fuel additives with detergent action frequently have
quaternized
nitrogen groups.
For example, WO 2006/135881 describes quaternized ammonium salts, prepared by
condensation of a hydrocarbyl-substituted acylating agent and of an oxygen or
nitrogen atom
containing compound with a tertiary amino group, and subsequent quaternization
by means
.. of hydrocarbyl epoxide in combination with stoichiometric amounts of an
acid, such as more
particularly acetic acid. These additives are used especially as diesel fuel
additives for
reducing power loss.
Polyalkene-substituted quaternized amines, such as more particularly
quaternized
polyisobuteneamines, and use thereof as detergent additives for reducing
intake valve
deposits, and as a lubricant additive for internal combustion engines, are
described in
US 2008/0113890.
US 6 331 648 B1 relates to specific quaternary etheramine compounds which
comprise a 1-
ethyl-1,3-propylene unit incorporated between alkoxylate chain and quaternary
nitrogen.
There is speculation as to the usability of these compounds as anticorrosion
or detergent
additives in gasoline and diesel fuels, but without any demonstration of the
usability thereof.
EP 182 669 Al describes halogen- or sulfur-containing alkoxylated quaternary
ammonium
compounds of the general structure
[RO(R1).CH2CH(R2)HNR3R4R61+ A-
where R1 is an alkylene oxide block. For these compounds, a whole series of
applications is
postulated, including general use as fuel and lubricant additives, but without
actually
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experimentally demonstrating specific functions. Preferred anions A- are
chloride,
methylsulfate and ethylsulfate.
US 4 564 372, US 4 581 151, US 4 600 409 and WO 1985/000620 relate to
5 polyoxyalkyleneamine salts quaternized, i.e. halogenated, with alkyl
halides, in which
polyoxyalkylene unit and amine unit via various linker groups, such as more
particularly
amine linker of the -C(0)-NH- type. Use as dispersants and corrosion
inhibitors in fuels is
postulated, but without actually experimentally demonstrating specific
functions.
It is therefore an object of the present invention to provide improved
quaternized fuel
additives which no longer have these disadvantages of the prior art and, more
particularly,
are usable both in diesel fuels and gasoline fuels.
Brief description of the invention:
It has now been found that, surprisingly, the above object is achieved by
provision of
specifically additized fuels and lubricants as defined in the appended claims.
The inventive
additives are superior in several ways over the known prior art additives and
can be used
both in diesel and gasoline fuels. They are notable for their advantageous
clean-up and
keep-clean effect on various components of internal combustion engines, such
as on diesel
engine injection nozzles, but also on intake valves and injectors of gasoline
engines, and
prevent the formation of combustion chamber deposits or eliminate combustion
chamber
deposits which have already formed from internal combustion engines. They
additionally
prevent the formation of deposits in fuel filters or eliminate filter
impurities which have already
formed.
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Description of figures:
Figure 1 shows the injector cleanliness achievable with inventive additives
after test
operation with a direct injection gasoline engine (lb and 1c) compared to
operation with
nonadditized fuel (la).
Figure 2 shows the course of a one-hour engine test cycle according to CEC F-
098-08.
Detailed description of the invention:
Al) Specific embodiments
The present invention relates particularly to the following specific
embodiments:
1. A fuel composition or lubricant composition, especially fuel
composition, comprising, in
a majority of a conventional fuel or lubricant, an effective amount of at
least one
reaction product comprising a quaternized nitrogen compound, or a component
fraction thereof which is obtained from the reaction product by purification
and
comprises a quaternized nitrogen compound, said reaction product being
obtainable
by reaction
a. of a polyether-substituted amine comprising at least one tertiary
quaternizable
amino group with
b. a quaternizing agent which converts the at least one tertiary amino group
to a
quaternary ammonium group.
2. The fuel composition or lubricant composition according to claim 1,
in which the
polyether substituent comprises monomer units of the general formula lc
-[-CH(R3)-CH(R4)-0-1- (lc)
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in which
R3 and Ritare the same or different and are each H, alkyl, alkylaryl or aryl.
3. The fuel composition or lubricant composition according to embodiment 2,
wherein the
polyether-substituted amine has a number-average molecular weight in the range
from
500 to 5000, especially 800 to 3000 or 900 to 1500.
=
4. The fuel composition or lubricant composition according to any of the
preceding
embodiments, wherein the quaternizing agent is selected from alkylene oxides,
optionally in combination with acid; aliphatic or aromatic mono- or
polycarboxylic
esters, such as more particularly mono- or dialkyl carboxylates; cyclic
nonaromatic or
aromatic mono- or polycarboxylic esters; dialkyl carbonates; alkyl sulfates;
alkyl
halides; alkylaryl halides; especially halogen- and sulfur-free quaternizing
agents, such
as alkylene oxides in combination with acid, for example a carboxylic acid;
aliphatic or
aromatic mono- or polycarboxylic esters, such as more particularly mono- or
dialkyl
carboxylates; cyclic nonaromatic or aromatic mono- or polycarboxylic esters
and
dialkyl carbonates; and mixtures thereof.
5. A fuel composition or lubricant composition comprising, in a majority of
a conventional
fuel or lubricant, an effective amount of at least one quaternized nitrogen
compound of
the general formula la or lb
(R5)(R1)(R2)NLA-0+CH(R3)-CH(R4)-OHTH (la)
X
RT-0-+CH(R3)-CH(R4)-0 _________________________________________
In...ICH(R3)¨CH(R4)¨N(R2)(Ri)(R5) (1b)
X
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in which
R1 and R2 are the same or different and are each alkyl, alkenyl, hydroxyalkyl,
hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R1 and R2 together are
alkylene,
oxyalkylene or aminoalkylene;
R3 and R4 are the same or different and are each H, alkyl, alkylaryl or aryl;
R5 is a radical introduced by quaternization, such as more particularly alkyl,
hydroxyalkyl, arylalkyl or hydroxyarylalkyl;
R6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in
each case
optionally substituted, for example by at least one hydroxyl radical or alkyl
radical, or
interrupted by at least one heteroatom;
A is a straight-chain or branched alkylene radical optionally interrupted by
one or more
heteroatoms, such as N, 0 and S;
n is an integer from 1 to 50 and
X- is an anion, especially an anion resulting from the quaternization
reaction.
6. The fuel composition or lubricant composition according to embodiment
5, in which
R1 and R2 are the same or different and are each Cl-C6-alkyl, hydroxy-C1-C6-
alkyl,
hydroxy-C1-C6-alkenyl, or amino-CI-Cs-alkyl, or R1 and R2 together form a C2-
C6-
alkylene, C2-C6-oxyalkylene or C2-C6-aminoalkylene radical;
R3 and R4 are the same or different and are each H, Ci-C6-alkyl or phenyl;
R5 is a radical introduced by quaternization, selected from C1-C6-alkyl,
hydroxy-Ci-C6-
alkyl or -CH2CH(OH)aryl;
R6 is Ci-C20-alkyl, for example C10-C20-, Cu-C20- or C12-C20-alkyl, or aryl or
alkylaryl,
where alkyl is especially Cl-C2o;
A is a straight-chain or branched C2-C6-alkylene radical optionally
interrupted by one or
more heteroatoms such as N, 0 and S;
n is an integer from 1 to 30 and
X- is an anion resulting from the quaternization reaction.
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7. The fuel composition according to any of the preceding embodiments,
selected from
diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasoline
fuels.
8. A quaternized nitrogen compound as defined in any of the preceding
embodiments,
selected especially from those which are free of halogen and sulfur.
9. A process for preparing quaternized nitrogen compounds of the general
formula la
(R5)(R1)(R2)N¨A-0+CH(R3)-CH(R4)-0 ________________ H (la)
X .-
in which
to R5, A, X and n are each as defined above
wherein
a. an aminoalkanol of the general formula II
(R1)(R2)N¨A¨OH (II)
in which
R1, R2 and A are each as defined above
is alkoxylated with an epoxide of the general formula Ill
0
(Ill)
(R3)HC ________________________________ CH(R4)
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in which
R3 and R4 are each as defined above
to obtain an alkoxylated amine of the formula
5
(Ri)(R2)N¨A-0+CH(R3)-CH(R4)-0+, = (la-1)
in which R1 to R4, A and n are each as defined above
and
b) the alkoxy compound of the formula la-1 thus obtained is
quaternized to obtain a
reaction product comprising at least one compound of the general formula la,
the
quaternization being effected, for example, with a compound of the general
formula IV
R5-X (IV)
in which
R5 is alkyl or aryl and X is as defined above, or with an alkylene oxide of
the formula
0
(IVa)
H2C __ CH(R5.)
in combination with an acid HX in which X is as defined above, where R5 is H,
alkyl or
aryl, and the R5 radical is a -CH2CH(OH)R5, group.
10. A process for preparing quaternized nitrogen compounds of the general
formula lb
Rj---O¨E-CH(R3)-CH(R4)-0 r¨h-TCH(R3)¨CH(R4)¨N(R2)(R1)(R5) (lb)
X
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in which R1 to R6, X and n are each as defined above,
wherein
a) an alcohol of the general formula V
R6-OH (V)
in which
R6 is as defined above is alkoxylated with an epoxide of the general formula
III
/0\ (III)
(R3)HC¨CH(R4)
in which
R3 and R4 are each as defined above to obtain a polyether of the formula lb-1;
R6---0-ECH(R3)-CH(R4)-0 in_l CH(R3)-CH(R4)0H (lb-1)
in which R3, R4 and R6, A, X and n are each as defined above,
b) then the polyether of the formula lb-1 thus obtained is aminated with an
amine of
the general formula
NH(Ri)(R2) (VII)
in which Ri and R2 are each as defined above
to obtain an amine of the formula lb-2
RO--ECH(R3)-CH(R4)-0-friTiCH(R3)-CH(R4)-N(R1)(R2) (lb-2)
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in which R1 to R4 and R5, A, X and n are each as defined above,
the amine of the formula (lb-2) is optionally alkylated if R1 and/or R2 is H,
and then
c) the product from stage b) is quaternized to obtain a reaction product
comprising
at least one compound of the general formula lb, the quaternization being
effected, for
example, with a compound of the general formula IV
R5-X (IV)
in which
R5 is alkyl or aryl and Xis as defined above, or with an alkylene oxide of the
formula
0
/ (IVa)
H2C¨CH(R5,)
in combination with an acid HX in which X is as defined above, where R5 is H,
alkyl or
aryl, and the R5 radical is a -CH2CH(OH)R5, group.
11. The process according to embodiment 9 or 10, wherein the quaternizing
agent is
selected from: alkylene oxides, optionally in combination with an acid; alkyl
carbonates, such as dialkyl carbonates; alkyl sulfates, such as dialkyl
sulfates; alkyl
phosphates, dialkyl phosphates, halides, such as alkyl or aryl halides;
aliphatic and
aromatic carboxylic esters, such as alkanoates, dicarboxylic esters; and
cyclic
aromatic or nonaromatic carboxylic esters.
12. A quaternized nitrogen compound obtainable by a process according to
embodiment
10 or 11, especially in halogen- and sulfur-free form.
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13. The use of a quaternized nitrogen compound according to embodiment 8 or
prepared
according to any of embodiments 9 to 11 as a fuel additive or lubricant
additive.
14. The use according to embodiment 12 as a diesel fuel additive, especially
as a cold flow
improver or wax antisettling additive (WASA).
15. The use according to embodiment 12 as a gasoline fuel additive for
reducing deposits
in the intake system of a gasoline engine, such as more particularly DISI and
PFI (Port
Fuel Injector) engines.
16. The use according to embodiment 12 as an additive for reducing fuel
consumption of
direct injection diesel engines, especially of diesel engines with common rail
injection
systems, and/or for minimizing power loss in direct injection diesel engines,
especially
in diesel engines with common rail injection systems, or as an additive for
reducing
and/or preventing deposits in the injection systems, such as more particularly
internal
diesel injector deposits (IDID), and/or for reducing and/or preventing
deposits in the
injection nozzles in direct injection diesel engines, especially in common
rail injection
systems.
17. An additive concentrate comprising, in combination with further diesel or
gasoline fuel
additives, especially diesel fuel additives, at least one quaternized nitrogen
compound
as defined in embodiment 8 or prepared according to either of embodiments 9
and 10.
In a specific configuration of the invention, in some or all of the above
embodiments, the
quaternizing agent is not an aromatic carboxylic ester, for example a
salicylic ester.
In a specific configuration of the invention, in some or all of the above
embodiments, the
quaternizing agent is selected from compounds of the formulae (1) and (2)
described herein.
14
In a specific configuration of the invention, in some or all of the above
embodiments, the
radical (nitrogen substituent) introduced by quaternization is especially
alkyl (especially Ci-
Cs-alkyl) or hydroxyarylalkyl (for example 2-hydroxy-2-phenylethyl).
In a specific configuration of the invention, in some or all of the above
embodiments, the
polyether substituent does not have any aryl or aralkyl groups.
In a specific configuration of the invention, in some or all of the above
embodiments, the
quaternized nitrogen compound is a compound of the formula (la) or (lb).
Test methods suitable in each case for examination of the applications
referred to above are
known to those skilled in the art, or are described in the experimental
section which follows.
A2) General definitions
"Halogen-free" or "sulfur-free" in the context of the present invention means
the absence of
inorganic or organic halogen or sulfur compounds and/or of the corresponding
ions thereof,
such as halide anions and sulfur-containing anions, such as more particularly
sulfates.
"Halogen-free" or "sulfur-free" comprises more particularly the absence of
stoichiometric
amounts of halogen or sulfur compounds or anions; substoichiometric amounts of
halogen or
sulfur compounds or anions are, for example, in molar ratios of less than
1:0.1, or less than
1:0.01 or 1:0.001, or 1:0.0001, of quaternized nitrogen compound to halogen or
sulfur
compound or ions thereof. "Halogen-free" or "sulfur-free" comprises, more
particularly, also
the complete absence of halogen or sulfur compounds and/or of the
corresponding ions
thereof, such as halide anion and sulfur-containing anions, such as more
particularly
sulfates.
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"Carboxylic acids" comprise, more particularly, organic carboxylic acids, such
as more
particularly monocarboxylic acids of the RCOOH type in which R is a short-
chain hydrocarbyl
radical, for example a lower alkyl- or Ci-C4alkylcarboxylic acid.
5 "Quaternizable" nitrogen groups or amino groups comprise especially
primary, secondary
and tertiary amino groups.
In the absence of statements to the contrary, the following general
definitions apply:
10 "Hydrocarbyl" should be interpreted broadly and comprises both cyclic
aromatic or
nonaromatic and long-chain or short-chain, straight or branched hydrocarbyl
radicals having
1 to 50 carbon atoms, which may optionally additionally contain heteroatoms,
for example 0,
N, NH, S, in the chain or ring thereof. Hydrocarbyl comprises, for example,
the alkyl, alkenyl,
aryl, alkylaryl, cycloalkenyl or cycloalkyl radicals defined hereinafter, and
the substituted
15 .. analogs thereof.
"Alkyl" or "lower alkyl" represents especially saturated, straight-chain or
branched
hydrocarbyl radicals having Ito 4, 1 to 6, 1 to 8, 1 to 10, Ito 14 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-ethy1-2-
methylpropyl; and
also n-heptyl, n-octyl, n-nonyl and n-decyl, n-dodecyl, n-tetradecyl, n-
hexadecyl, 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
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hydroxyalkyl groups, for example those with a primary (terminal) hydroxyl
group, such as
hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those with
nonterminal
hydroxyl groups, such as 1-hydroxyethyl, 1-or 2-hydroxypropyl, 1- or 2-
hydroxybutyl or 1-, 2-
or 3-hydroxybutyl.
"Alkenyl" represents mono- or polyunsaturated, especially monounsaturated,
straight-chain
or branched hydrocarbyl radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2
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-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-
pentenyl, 4-
pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-
2-butenyl, 2-
methy1-2-butenyl, 3-methyl-2-butenyl, 1-methy1-3-butenyl, 2-methyl-3-butenyl,
3-methy1-3-
butenyl, 1,1-dimethy1-2-propenyl, 1,2-dimethy1-1-propenyl, 1,2-dimethy1-2-
propenyl, 1-ethy1-1-
propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-
hexenyl, 1-
methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methy1-1-
pentenyl, 1-methyl-
2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-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-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-
dimethy1-2-
butenyl, 1,1-dimethy1-3-butenyl, 1,2-dimethy1-1-butenyl, 1,2-dimethy1-2-
butenyl, 1,2-dimethyl-
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-
ethy1-2-butenyl,
1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,
1,1,2-trimethy1-2-
propenyl, 1-ethyl-1-methy1-2-propenyl, 1-ethy1-2-methy1-1-propenyl and 1-ethy1-
2-methy1-2-
propenyl.
"Hydroxyalkenyl" represents especially the mono- or polyhydroxylated,
especially
monohydroxylated, analogs of the above alkenyl radicals.
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"Aminoalkyl" and "aminoalkenyl" are especially the mono- or polyaminated,
especially
monoaminated, analogs of the above alkyl and alkenyl radicals respectively, or
analogs of
the above hydroxyalkyl where the OH group is replaced by an amino group.
"Alkylene" represents straight-chain or singly or multiply branched
hydrocarbylene bridging
groups having 1 to 10 carbon atoms, for example Ci-C7alkylene groups selected
from -CH2-,
-(CH2)2-, -(CH2)3-,-(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-C4-
alkylene groups selected from -CH2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)2-
CH(CH3)-, -CH2-
CH(CH3)-CH2- or C2-Cs-alkylene groups, for example -CH2-CH(CH3)-, -CH(CH3)-CH2-
, -
CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CH2-C(CH3)2-, -C(CH3)2-CH(CH3)-, -CH(CH3)-
C(CH3)2-, -
CH2-CH(Et)-, -CH(CH2CH3)-CH2-, -CH(CH2CH3)-CH(CH2CH3)-, -C(CH2CH3)2-CH2-, -CH2-
C(CH2CH3)2-, -CH2-CH(n-propyI)-, -CH(n-propyI)-CH2-, -CH(n-propyI)-CH(CH3)-, -
CH2-CH(n-
buty1)-, -CH(n-butyl)-CH2-, -CH(CH3)-CH(CH2CH3)-, -CH(CH3)-CH(n-propyI)-, -
CH(CH2CH3)-
CH(CH3)-, -CH(CH3)-CH(CH2CH3)-, or 02-C4-alkylene groups, for example selected
from -
(CH2)2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CH2-
C(CH3)2-,
-CH2-CH(CH2CH3)-', -CH(CH2CH3)-CH2-.
Oxyalkylene radicals correspond to the definition of the above straight-chain
or singly or
multiply branched alkylene radicals having 2 to 10 carbon atoms, where the
carbon chain is
interrupted once or more than once, especially once, by an oxygen heteroatom.
Nonlimiting
examples include: -CH2-0-CH2-, -(CH2)2-0-(CH2)2-, -(CH2)3-0-(CH2)3-, or -CH2-0-
(CH2)2-, -
(CH2)2-0-(CH2)3-, -CH2-0-(CH2)3.
"Aminoalkylene" corresponds to the definition of the above straight-chain or
singly or multiply
branched alkylene radicals having 2 to 10 carbon atoms, where the carbon chain
is
interrupted once or more than once, especially once, by a nitrogen group
(especially -NH-
group). Nonlimiting examples include: -CH2-NH-CH2-, -(CH2)2-NH-(CH2)2-, -
(CH2)3-NH-
(CH2)3-, or -CH2-NH-(CH2)2-, -(CH2)2-NH-(CH2)3-, -CH2-NH-(CH2)3.
CA 02854421 2014-05-02
18
"Alkenylene" is the mono- or polyunsaturated, especially monounsaturated,
analog of the
above alkylene groups having 2 to 10 carbon atoms, especially C2-C7-
alkenylenes or C2-C4-
alkenylene, such as -CH=CH-, -CH=CH-CH2-, - CH2-CH=CH-, -CH=CH-CH2-CH2-, -CH2-
CH=CH-CH2-, -CH2-CH2-CH=CH-, -CH(CH3)-CH=CH-, -CH2-C(CH3)=CH-.
"Cycloalkyl" represents carbocyclic radicals having 3 to 20 carbon atoms, for
example C3-
C12-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferably
cyclopentyl,
cyclohexyl, cycloheptyl; and 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 attachment
to the rest of the molecule may be via any suitable carbon atom.
"Cycloalkenyl" or "mono- or polyunsaturated cycloalkyl" represents especially
monocyclic
mono- or polyunsaturated hydrocarbyl groups having 5 to 8 and preferably to 6
carbon ring
members, for example the monounsaturated cyclopehten-1-yl, cyclopenten-3-yl,
cyclohexen-
1 -yl, cyclohexen-3-y1 and cyclohexen-4-y1 radicals.
"Aryl" represents mono- or polycyclic, preferably mono- or bicyclic,
optionally substituted
aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for
example phenyl,
biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl,
indenyl and
phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5 or 6
identical or different
substituents.
"Alkylaryl" represents the alkyl-substituted analogs of the above aryl
radicals mono- or
polysubstituted, especially mono- or disubstituted, in any ring position,
where aryl is likewise
as defined above, for example C1-C4-alkylphenyl where the C1-C4-alkyl radicals
may be in
any ring position.
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"Substituents" for radicals specified herein are especially selected from keto
groups, -COOH,
-COO-alkyl, -OH, -SH, -CN, amino, -NO2, alkyl, or alkenyl groups.
Mn (number-average molecular weight) is determined in a conventional manner;
more
particularly, the figures relate to values determined by gel permeation
chromatography or
mass spectrometry.
A3) Starter compounds (alcohols of the formula V and amino alcohols of the
formula II)
a) alcohols of the general formula V
R6-0H (V)
in which R6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl,
aryl, in each
case optionally substituted, for example by at least one hydroxyl radical or
alkyl radical, or
interrupted by at least one heteroatom;
b) amino alkanols of the general formula II
(R1)(R2)N¨A¨OH (II)
in which
F21 and R2 are the same or different and are each alkyl, alkenyl,
hydroxyalkyl, hydroxyalkenyl,
aminoalkyl or aminoalkenyl, or R1 and R2 together are alkylene, oxyalkylene or
aminoalkylene; and
A is a straight-chain or branched alkylene or alkenylene radical optionally
interrupted by one
or more heteroatoms, such as N, 0 and S.
CA 02854421 2014-05-02
A4) Quaternizing agents:
Useful quaternizing agents in principle include all compounds suitable as
such. The
quaternizing agent is especially selected from alkylene oxides, optionally in
combination with
5 acid; aliphatic or aromatic carboxylic esters, such as more particularly
dialkyl carboxylates;
alkanoates; cyclic nonaromatic or aromatic carboxylic esters; dialkyl
carbonates; alkyl
sulfates; alkyl halides; alkylaryl halides; and mixtures thereof.
In a particular embodiment, however, the at least one quaternizable tertiary
nitrogen atom is
10 quaternized with at least one quaternizing agent selected from epoxides,
especially
hydrocarbyl epoxides:
a a
a'11> X1 a
15 in which the Ra radicals present therein are the same or different and
are each = H or a
hydrocarbyl radical. The hydrocarbyl radical may have at least 1 to 14 carbon
atoms. In
particular, these are aliphatic or aromatic radicals, for example linear or
branched C1.C.4-alkyl
radicals, or aromatic radicals, such as phenyl or C1-C4-alkylphenyl.
20 Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic
alkylene oxides, such
as especially C2_16-alkylene oxides, such as ethylene oxide, propylene oxide,
1,2-butylene
oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1,2-
pentene oxide,
2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-
hexene oxide,
2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-
butene oxide,
3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-
1,2-pentene
oxide; tetradecane oxide; hexadecene oxide; and also aromatic-substituted
ethylene oxides,
such as optionally substituted styrene oxide, especially styrene oxide or 4-
methylstyrene
oxide.
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21
In the case of use of epoxides as quaternizing agents, they are used in the
presence or in
the absence of free acids, especially in the presence or absence of free
protic acids, such as
in particular with C1-12-monocarboxylic acids such as formic acid, acetic acid
or propionic
.. acid, or 02.12-dicarboxylic acids such as oxalic acid or adipic acid; or
else in the presence or
absence of sulfonic acids such as benzenesulfonic acid or toluenesulfonic
acid, or aqueous
mineral acids such as sulfuric acid or hydrochloric acid. The quaternization
product thus
prepared is thus either "acid-containing" or "acid-free" in the context of the
present invention.
A further group of quaternizing agents includes especially alkyl esters 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, the quaternization of the at least one
quaternizable tertiary
nitrogen atom is effected, however, with at least one quaternizing agent
selected from
a) compounds of the general formula 1
R10C(0)R2 (1)
in which
R1 is a lower alkyl radical and
R2 is an optionally substituted monocyclic aryl or cycloalkyl radical,
where the substituent
is selected from OH, NH2, NO2, C(0)0R3; Ria0C(0)- in which Ria is as defined
above for R1,
and R3 is H or R1;
or
b) compounds of the general formula 2
R10C(0)-A-C(0)0Ria (2)
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22
in which
R1 and Ria are each independently a lower alkyl radical and
A is hydrocarbylene (such as alkylene or alkenylene).
Especially suitable quaternizing agents include the lower alkyl esters of
oxalic acid, such as
dimethyl oxalate and diethyl oxalate.
Particularly suitable compounds of the formula 1 are those in which
R1 is a Cl-, 02- or C3-alkyl radical and
R2 is a substituted phenyl radical where the substituent represents HO-
or an ester radical
of the formula R130C(0)- which is in the para, meta or especially ortho
position to the
R10C(0)- radical on the aromatic ring.
Especially suitable quaternizing agents include 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.
An "anion resulting from the quaternization reaction" X- is, for example, a
halide, for example
a chloride or bromide, a sulfate radical ((SO4)2-) or the anionic radical of a
mono- or
polybasic, aliphatic or aromatic carboxylic acid, or the anionic radical
ROC(0)0- resulting
from the quaternization reaction of a dialkyl carbonate.
A5) Quaternizable nitrogen compounds (of the formula II):
The quaternizable nitrogen compound is selected from hydroxyalkyl-substituted
mono- or
polyamines having at least one quaternizable primary, secondary or tertiary
amino group and
at least one hydroxyl group which can be joined to a polyether radical.
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The quaternizable nitrogen compound is especially selected from hydroxyalkyl-
substituted
primary, secondary, tertiary and quaternary monoamines, and hydroxyalkyl-
substituted
primary, secondary, tertiary and quaternary diamines.
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.
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 different
and are also as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-
hydroxypropyl or
4-hydroxybutyl; alkylene is especially ethylene, propylene or butylene.
Mention should be made especially of the following quaternizable nitrogen
compounds:
CA 02854421 2014-05-02
24
NAME FORMULA
Alcohols with primary and secondary amine
Ethanolamine H 2
OH
3-Hydroxy-1-propylamine H2N
HON1
Diethanolamine
OH
HON
Diisopropanolamine
OH
N-(2-Hydroxyethyl)ethylenediamine NH2
HO
Alcohols with tertiary amine
OH
Triethanolamine, (2,21,211-nitrilotriethanol)
HON
OH
H0`.7-The
1-(3-Hydroxypropyl)imidazole L
HO /--0H
\--N
Tris(hydroxymethyl)amine
\--OH
CA 02854421 2014-05-02
3-Dimethylamino-1-propanol 1
-,' ...õ.............-.........NOH
3-Diethylamino-1-propanol HO-Nj
HO/ -
2-Dimethylamino-1-ethanol N.,...N....-
I
,
4-Diethylamino-1-butanol HO.,,, Nj
A6) Preparation of inventive additives:
5 a) Preparation of the polyether-substituted quaternizable intermediates
(la-1 and lb-1)
al) Proceeding from amino alcohols of the formula II:
The amino alcohols of the general formula II can be alkoxylated in a manner
known in
10 principle to obtain an alkoxylated amine of the general formula la-1.
The performance of alkoxylations is known in principle to those skilled in the
art. It is likewise
known to those skilled in the art that the reaction conditions, especially the
selection of the
catalyst, can influence the molecular weight distribution of the alkoxylates.
For the alkoxylation, C2-C16-alkylene oxides are used, for example ethylene
oxide, propylene
oxide or butylene oxide. Preference is given in each case to the 1,2-alkylene
oxides.
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26
The alkoxylation may be a base-catalyzed alkoxylation. For this purpose, the
amino alcohols
(II) can be admixed in a pressure reactor with alkali metal hydroxides,
preferably potassium
hydroxide, or with alkali metal alkoxides, for example sodium methoxide. Water
still present
in the mixture can be drawn off by means of reduced pressure (for example <
100 mbar)
and/or increased temperature (30 to 150 C). Thereafter, the alcohol is present
as the
corresponding alkoxide. Subsequently, inert gas (e.g. nitrogen) is used for
intertization and
the alkylene oxide(s) is/are added stepwise at temperatures of 60 to 180 C up
to a pressure
of max. 10 bar. At the end of the reaction, the catalyst can be neutralized by
adding acid (e.g.
acetic acid or phosphoric acid) and can be filtered off if required. The basic
catalyst can also
be neutralized by adding commercial magnesium silicates, which are
subsequently filtered
off. Optionally, the alkoxylation can also be performed in the presence of a
solvent. This may
be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.
The alkoxylation of the amino alcohols can also be undertaken by means of
other methods,
for example by acid-catalyzed alkoxylation. In addition, it is possible to
use, for example,
double hydroxide clays as described in DE 43 25 237 Al, or it is possible to
use double
metal cyanide catalysts (DMC catalysts). Suitable DMC catalysts are disclosed,
for example,
in DE 102 43 361 Al, especially paragraphs [0029] to [0041], and literature
cited therein. For
example, it is possible to use catalysts of the Zn-Co type. To perform the
reaction, the amino
alcohol can be admixed with the catalyst, and the mixture can be dewatered as
described
above and reacted with the alkylene oxides as described. Typically not more
than 1000 ppm
of catalyst based on the mixture are used, and due to this small amount the
catalyst can
remain in the product. The amount of catalyst may generally be less than 1000
ppm, for
example 250 ppm or less.
The alkoxylation can alternatively also be undertaken by reaction of compounds
(IV) and (V)
with cyclic carbonates, for example ethylene carbonate.
CA 02854421 2014-05-02
27
a2) Proceeding from alkanols of the formula V:
As described in the above section al) for amino alcohols (II), it is
analogously also possible
to alkoxylate alkanols R6OH in a manner known in principle to give polyethers
(lb-1). The
polyethers thus obtained can subsequently be converted to the corresponding
polyetheramines (lb-2) by reductive amination with ammonia, primary amines or
secondary
amines (VII) by customary methods in continuous or batchwise processes using
hydrogenation or amination catalysts customary therefor, for example those
comprising
catalytically active constituents based on the elements Ni, Co, Cu, Fe, Pd,
Pt, Ru, Rh, Re, Al,
Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo, W or combinations of these
elements with one
another, in customary amounts. The reaction can be performed without solvent
or, in the
case of high polyether viscosities, in the presence of a solvent, preferably
in the presence of
branched aliphatics, for example isododecane. The amine component (VII) is
generally used
in excess, for example in a 2- to 100-fold excess, preferably 10- to 80-fold
excess. The
reaction is performed at pressures of 10 to 600 bar over a period of 10
minutes to 10 hours.
After cooling, the catalyst is removed by filtration, excess amine component
(VII) is vaporized
and the water of reaction is distilled off azeotropically or under a gentle
nitrogen stream.
Should the resulting polyetheramine (lb-2) have primary or secondary amine
functionalities
(R1 and/or R2 is H), it can subsequently be converted to a polyetheramine with
tertiary amine
function (R1 and R2 not H). The alkylation can be effected in a manner known
in principle by
reaction with alkylating agents. All alkylating agents are suitable in
principle, for example
alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides,
optionally in combination with
acid; aliphatic or aromatic carboxylic esters, such as more particularly
dialkyl carboxylates;
alkanoates; cyclic nonaromatic or aromatic carboxylic esters; dialkyl
carbonates; and
mixtures thereof. The reactions to give the tertiary polyetheramine may also
take place by
reductive amination, by reaction with a carbonyl compound, for example
formaldehyde, in
the presence of a reducing agent. Suitable reducing agents are formic acid or
hydrogen in
the presence of a suitable heterogeneous or homogeneous hydrogenation
catalyst. The
reactions can be performed without solvent or in the presence of solvents.
Suitable solvents
CA 02854421 2014-05-02
28
are, for example, H20, alkanols such as methanol or ethanol, or 2-
ethylhexanol, aromatic
solvents such as toluene, xylene or solvent mixtures of the Solvesso series,
or aliphatic
solvents, especially mixtures of branched aliphatic solvents. The reactions
are performed at
temperatures of 10 C to 300 C at pressures of 1 to 600 bar over a period of 10
minutes to
10 h. The reducing agent is used at least in a stoichiometric amount,
preferably in excess,
especially in a 2- to 10-fold excess.
The reaction product thus formed (polyetheramine lb-1 or lb-2) can
theoretically be purified
further, or the solvent can be removed. Usually, however, this is not
absolutely necessary,
such that the reaction product can be transferred without further purification
into the next
synthesis step, the quaternization.
b) Quaternization
b1) with epoxide/acid
To perform the quaternization, the reaction product or reaction mixture from
the above stage
a) is admixed with at least one epoxide compound of the above formula (IVa),
especially in
the stoichiometric amounts required to achieve the desired quaternization. The
acid is
preferably likewise added in stoichiometric amounts. It is possible to use,
for example, 0.1 to
2.0 equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent per
equivalent of
quaternizable tertiary nitrogen atom. More particularly, however,
approximately equimolar
proportions of the epoxide are used to quaternize a tertiary amine group.
Correspondingly
higher use amounts are required to quaternize a secondary or primary amine
group. Suitable
acids are especially carboxylic acids, for example acetic acid.
Typical working temperatures here are in the range from 15 to 160 C,
especially from 20 to
150 or 40 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 bar. The pressure is
generally
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29
determined by the vapor pressure of the alkylene oxide used at the particular
reaction
temperature. More particularly, an inert gas atmosphere, for example nitrogen,
is
appropriate.
If required, the reactants can be initially charged for the epoxidation in a
suitable 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. Alkanols are additionally suitable as solvents or
cosolvents in a
mixture with the aforementioned solvents, for example methanol, ethanol,
propanol, 2-
ethylhexanol or 2-propylheptanol.
b2) with compounds of the formula IV
To perform the quaternization, the reaction product or reaction mixture from
the above stage
.. a) is admixed with at least one alkylating agent of the formula (IV),
especially in the
stoichiometric amounts required to achieve the desired quaternization. For
each equivalent
of quaternizable tertiary nitrogen atom, it is possible to use, for example,
0.1 to 5.0
equivalents, or 0.5 to 2.0 equivalents, of quaternizing agent. More
particularly, however,
approximately equimolar proportions of the alkylating agent are used to
quaternize a tertiary
amine group. Correspondingly higher use amounts are required to quaternize a
secondary or
primary amine group. Particularly suitable quaternizing agents are methyl
salicylate, dimethyl
oxalate, dimethyl phthalate and dimethyl carbonate.
The reaction can optionally be accelerated by adding catalytic or
stoichiometric amounts of
an acid. Suitable acids are, for example, proton donors such as aliphatic or
aromatic
carboxylic acids or fatty acids. Additionally suitable are Lewis acids, for
example boron
trifluoride, ZnC12, MgCl2, AlC13 or FeCl3. The acid can be used in amounts of
0.01 to 50% by
weight, for example in the range of 0.1 to 10% by weight.
CA 02854421 2014-05-02
Typically, temperatures are employed here in the range from 15 to 160 C,
especially from 20
to 150 or 40 to 140 C. The reaction time may be in the region of a few minutes
or a few
hours, for example about 10 minutes up to about 24 hours. The reaction can be
effected at
pressure about 0.1 to 20 bar, for example 0.5 to 10 bar. More particularly,
the reaction can
5 be effected at standard pressure. More particularly, an inert gas
atmosphere, for example
nitrogen, is appropriate.
If required, the reactants can be initially charged in a suitable organic
aliphatic or aromatic
solvent or a mixture thereof for the quaternization, or a sufficient
proportion of solvent from
10 reaction step a) is still present. Typical examples are, for example,
solvents of the Solvesso
series, toluene or xylene. Alkanols are additionally suitable as solvents or
as cosolvents in a
mixture with the aforementioned solvents, for example methanol, ethanol,
propanol, butanol,
2-ethylhexanol or 2-propylheptanol.
15 c) Workup of the reaction mixture
The reaction end product thus formed can theoretically be purified further, or
the solvent can
be removed. This is customary but not absolutely necessary, and so the
reaction product can
be used without further purification as an additive, optionally after blending
with further
20 additive components (see below). Optionally, the acid used can be
removed from the
reaction product by filtration, neutralization or extraction. Optionally, an
excess of alkylating
agent can be removed by distillation or by filtration.
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.
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31
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:
B1) Detergent additives
The customary detergent additives are preferably amphiphilic substances which
possess at
least one hydrophobic hydrocarbyl radical with a number-average molecular
weight (Mn) 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;
CA 02854421 2014-05-02
32
(Df) polyoxy-C2- to Ca-alkylene moieties terminated by hydroxyl groups, mono-
or
polyamino groups, at least one nitrogen atom having basic properties, or by
carbamate
groups;
(Dg) carboxylic ester groups;
(Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino
and/or
amido and/or imido groups; and/or
.. (Di) moieties obtained by Mannich reaction of substituted phenols with
aldehydes and
mono- or polyamines.
The hydrophobic hydrocarbyl radical in the above detergent additives, which
ensures the
adequate solubility in the fuel, has a number-average molecular weight (Mn) 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. Typical hydrophobic hydrocarbyl radicals,
especially in conjunction
with the polar moieties, include especially polypropenyl, polybutenyl and
polyisobutenyl
radicals with a number-average molecular weight Mn of preferably in each case
300 to 5000,
more preferably 300 to 3000, even more preferably 500 to 2500, even more
especially
preferably 700 to 2500 and especially 800 to 1500.
Examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Da) are preferably
polyalkenemono- or
polyalkenepolyamines based on polypropene or on high-reactivity (i.e. having
predominantly
terminal double bonds) or conventional (i.e. having predominantly internal
double bonds)
polybutene or polyisobutene having Mn = 300 to 5000, more preferably 500 to
2500 and
especially 700 to 2500. Such additives based on high-reactivity polyisobutene,
which can be
prepared from the polyisobutene which may comprise up to 20% by weight of n-
butene units
CA 02854421 2014-05-02
33
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 6 and y positions) are used as starting materials in the preparation of
the additives, a
possible preparative route is by chlorination and subsequent amination or by
oxidation of the
double bond with air or ozone to give the carbonyl or carboxyl compound and
subsequent
amination under reductive (hydrogenating) conditions. The amines used here for
the
amination may be, for example, ammonia, monoamines or the abovementioned
polyamines.
Corresponding additives based on polypropene are described in particular in WO-
A 94/24231.
Further particular additives comprising monoamino groups (Da) are the
hydrogenation
products of the reaction products of polyisobutenes having an average degree
of
polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and oxygen,
as described 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 20 262.
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,6-
dinitropolyisobutene) and mixed
hydroxynitropolyisobutenes (e.g. a-nitro-6-hydroxypolyisobutene).
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34
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 Co-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.
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, Ci- to C30-alkylcyclohexanols
or Ci- to C30-
alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or
butylene oxide
per hydroxyl group or amino group and, in the case of the polyetheramines, by
subsequent
reductive amination with ammonia, monoamines or polyamines. Such products are
described
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
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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
5 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,
10 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
15 derivatives of alkyl- or alkenyl-substituted succinic anhydride and
especially the
corresponding derivatives of polyisobutenylsuccinic anhydride which are
obtainable by
reacting conventional or high-reactivity polyisobutene having Mn = preferably
300 to 5000,
more preferably 300 to 3000, even more preferably 500 to 2500, even more
especially
preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a
thermal route
20 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
25 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
30 documents (1) and (2). They are preferably the reaction products of
alkyl- or alkenyl-
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36
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.
One or more of the detergent additives mentioned can be added to the fuel in
such an
amount that the dosage of these detergent additives is preferably 25 to 2500
ppm by weight,
especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight.
B2) Carrier oils
Carrier oils additionally used may be of mineral or synthetic nature. Suitable
mineral carrier
oils are the fractions obtained in crude oil processing, such as brightstock
or base oils having
viscosities, for example, from the SN 500 to 2000 class; but also aromatic
hydrocarbons,
paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction
which is obtained in
the refining of mineral oil and is known as "hydrocrack oil" (vacuum
distillate cut having a
boiling range 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 carrier oils.
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37
Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins
or
polyinternalolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic
polyether-amines,
alkylphenol-started polyethers, alkylphenol-started polyetheramines and
carboxylic esters 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).
Examples of suitable polyethers or polyetheramines are preferably compounds
comprising
polyoxy-C2- to C4-alkylene moieties which are obtainable by reacting C2- to
C60-alkanols, C6-
to C30-alkanediols, mono- or di-C2- to C30-alkylamines, Ci- to C30-
alkylcyclohexanols or 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
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. For example, the polyetheramines used may be poly-C2- to C6-
alkylene oxide
amines or functional derivatives thereof. Typical examples thereof are
tridecanol butoxylates
or isotridecanol butoxylates, isononylphenol butoxylates and also
polyisobutenol butoxylates
and propoxylates, and also the corresponding reaction products with ammonia.
Examples of carboxylic esters of long-chain alkanols are 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.
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38
Examples of particularly suitable synthetic carrier oils are alcohol-started
polyethers having
about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and
especially 15 to 30 C3-
to C6-alkylene oxide units, for example 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 C6- to GIs-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 C3- to C6-alkylene oxides.
Examples of
monohydric aliphatic C6-C18-alcohols are hexanol, heptanol, octanol, 2-
ethylhexanol, nonyl
alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol,
tetradecanol,
pentadecanol, hexadecanol, octadecanol and the constitutional and positional
isomers
thereof. The alcohols can be used either in the form of the pure isomers or in
the form of
technical grade mixtures. A particularly preferred alcohol is tridecanol.
Examples of 03- to 06-
alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene
oxide, such as
1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran,
pentylene oxide
and hexylene oxide. Particular preference among these is given to C3- to C4-
alkylene oxides,
i.e. propylene oxide such as 1,2-propylene oxide and butylene oxide such as
1,2-butylene
oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is
used.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, as
described in
DE-A 10 102 913.
Particular carrier oils are synthetic carrier oils, particular preference
being given to the above-
described alcohol-started polyethers.
The carrier oil or the mixture of different carrier oils is added to the fuel
in an amount of
preferably 1 to 1000 ppm by weight, more preferably of 10 to 500 ppm by weight
and
especially of 20 to 100 ppm by weight.
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39
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.
The cold flow improver is typically selected from:
(K1) copolymers of a C2- to Cc-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 Cc-olefin monomers for the copolymers of class (K1) are, for
example, those
having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably
1 or 2 carbon-
carbon double bonds, especially having one carbon-carbon double bond. In the
latter case,
the carbon-carbon double bond may be arranged either terminally (a-olefins) or
internally.
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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
5 preferably selected from alkenyl carboxylates, (meth)acrylic esters and
further olefins.
When further olefins are also copolymerized, they are preferably higher in
molecular weight
than the abovementioned C2- to C40-olefin base monomer. When, for example, the
olefin
base monomer used is ethylene or propene, suitable further olefins are in
particular Cio- to
10 C40-a-olefins. Further olefins are in most cases only additionally
copolymerized when
monomers with carboxylic ester functions are also used.
Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid
with C1- to C20-
alkanols, especially Ci- to C10-alkanols, in particular with methanol,
ethanol, propanol,
15 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, C2- to C14-alkenyl esters, for
example the
vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms,
whose
20 hydrocarbyl radical may be linear or branched. Among these, preference
is given to the vinyl
esters. Among the carboxylic acids with a branched hydrocarbyl 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 hydrocarbyl 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
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41
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 C2- to Cava-olefin, a C1- to C20-alkyl ester of an
ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a C2- to C14-alkenyl ester
of a
saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as
copolymers
of class (K1). Terpolymers of this kind are described in WO 2005/054314. A
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
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.
The copolymers of class (K1) preferably have a number-average molecular weight
Mn of
1000 to 20 000, 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 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
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42
esterified copolymers of styrene and fumaric acid. Suitable comb polymers may
also be
polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also
suitable
comb polymers. Comb polymers suitable as components of class (K2) are, for
example, also
those described in WO 2004/035715 and in "Comb-Like Polymers. Structure and
Properties",
N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117
to 253
(1974)". Mixtures of comb polymers are also suitable.
Polyoxyalkylenes suitable as components of class (K3) are, for example,
polyoxyalkylene
esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and
mixtures thereof.
These polyoxyalkylene compounds preferably comprise at least one linear alkyl
group,
preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms
and a
polyoxyalkylene group having a number-average molecular weight of up to 5000.
Such
polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also
in
US 4,491,455. Particular polyoxyalkylene compounds are based on polyethylene
glycols and
polypropylene glycols having a number-average molecular weight of 100 to 5000.
Additionally suitable are polyoxyalkylene mono- and diesters of fatty acids
having 10 to 30
carbon atoms, such as stearic acid or,behenic acid.
Polar nitrogen compounds suitable as components of class (K4) may be either
ionic or
nonionic and preferably have at least one substituent, 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 C40-
hydrocarbyl radical. The nitrogen substituents may also be quaternized, i.e.
be in cationic
form. An example of such nitrogen compounds is that of ammonium salts and/or
amides
which are obtainable by the reaction of at least one amine substituted by at
least one
hydrocarbyl 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 C8- to
C40-alkyl radical.
Primary amines suitable for preparing the polar nitrogen compounds mentioned
are, for
example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine,
tetradecylamine and the higher linear homologs. Secondary amines suitable for
this purpose
are, for example, dioctadecylamine and methylbehenylamine. Also suitable for
this purpose
CA 02854421 2014-05-02
44
in which the variable A is a straight-chain or branched C2- to C6-alkylene
group or the moiety
of the formula III
B CH2-CH2-
HOOCõN-
1
CH2-CH2-
(III)
and the variable B is a Ci- to Cis-alkylene group. The compounds of the
general formulae ha
and II b especially have the properties of a WASA.
Moreover, the preferred oil-soluble reaction product of component (K4),
especially that of the
general formula ha or Ilb, is an amide, an amide-ammonium salt or an ammonium
salt in
which no, one or more carboxylic acid groups have been converted to amide
groups.
Straight-chain or branched C2- to C6-alkylene groups of the variable A are,
for example, 1,1-
ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-
butylene, 2-methyl-
1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethy1-1,3-
propylene, 1,6-
hexylene (hexamethylene) and in particular 1,2-ethylene. The variable A
comprises
preferably 2 to 4 and especially 2 or 3 carbon atoms.
C1- to Cig-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
hydrocarbyl
radicals which may optionally be bonded to one another.
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These parent amines of the oil-soluble reaction products of component (K4) are
usually
secondary amines and have the general formula HN(R8)2 in which the two
variables R8 are
each independently straight-chain or branched Cio- to C30-alkyl radicals,
especially C14- to
C24-alkyl radicals. These relatively long-chain alkyl radicals are preferably
straight-chain or
5 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
10 .. 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.
15 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
20 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
25 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.
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46
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 C14 and C15 alcohols, the acid groups having
been neutralized
with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described,
for example, in
WO 00/44857.
The cold flow improver or the mixture of different cold flow improvers is
added to the middle
distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm
by weight, more
preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm
by weight
and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by
weight.
B4) Lubricity improvers
Suitable lubricity improvers or friction modifiers are based typically on
fatty acids or fatty acid
esters. Typical examples are tall oil fatty acid, as described, for example,
in WO 98/004656,
and glyceryl monooleate. The reaction products, described in US 6 743 266 B2,
of natural or
47
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 (Rhein Chemie Mannheim,
Germany) or
HiTEC TM 536 (Ethyl Corporation).
B6) Dem ulsifiers
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
(ED) and
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 NALCOTM 7D07 (Nalco) and
TOLADTm
2683 (Petrolite).
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B8) Antifoams
Suitable antifoams are, for example, polyether-modified polysiloxanes, for
example the
products available under the trade names TEGOPRENTm 5851 (Goldschmidt), Q
25907 (Dow
Corning) and RHODOSIL (Rhone Poulenc).
B9) Cetane number improvers
Suitable cetane number improvers are, for example, aliphatic nitrates such as
2-ethylhexyl
nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
B10) Antioxidants
Suitable antioxidants are, for example substituted phenols, such as 2,6-di-
tert-butylphenol and
6-di-tert-butyl-3-methylphenol, and also phenylenediamines such as N,N'-di-sec-
butyl-p-
phenylenediamine.
B11) Metal deactivators
Suitable metal deactivators are, for example, salicylic acid derivatives such
as
N,N'-disalicylidene-1,2-propanediamine.
B12) Solvents
Suitable solvents are, for example, nonpolar organic solvents such as aromatic
and aliphatic
hydrocarbons, for example toluene, xylenes, white spirit and products sold
under the trade
names SHELLSOL (Royal Dutch/Shell Group) and 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.
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49
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.
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 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.).
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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
5 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
10 fatty acids which derive from vegetable and/or animal oils and/or fats.
Alkyl esters are
typically understood to mean lower alkyl esters, especially CI-Ca-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
15 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
20 content, i.e. having a sulfur content of less than 0.05% by weight,
preferably of less than
0.02% by weight, more particularly of less than 0.005% by weight and
especially of less than
0.001% by weight of sulfur.
Useful gasoline fuels include all commercial gasoline fuel compositions. One
typical
25 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.
51
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. Especially the
test methods specified hereinafter form part of the general disclosure of the
application and
are not limited to the specific working examples.
Experimental section:
A. General test methods
1. XUD9 test ¨ determination of flow restriction
The procedure was according to the standard stipulations of CEC F-23-1-01.
2. DW10 test ¨ determination of power loss as a result of injector deposits
in the common
rail diesel engine
2.1. DW10-KC ¨ keep-clean test
The keep-clean test is based on CEC test procedure F-098-08 Issue 5. This is
done using the
same test setup and engine type (PEUGEOTTm DW10 ) as in the CEC procedure.
Change and special features:
In the tests, cleaned injectors were used. The cleaning time in the ultrasound
bath in water +
10% Superdecontamine (Intersciences, Brussels) at 60 C was 4 h.
Test run times:
The test run time was 12 h without shutdown phases. The one-hour test cycle
from CEC F-
098-08, shown in figure 2 and table 1 below, was run through 12 times.
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51a
Table 1
step duration engine speed load torque boost air after IC ..
(minutes) (rpm) (0/0) (Nm) ( C)
+/- 20 +/-5 +/-3
i ,
1
- 1750 (201 62 45
, -.÷
- 3000 (60) 173 50
$ lt 150 (20) 62 45
_
4 '71 3500 (SO) 212 50
1, 1750 (20) 62 45
_
6 10 4000 100 i 50
7 1. 1250 (10) 25 43**
-
S 7. 3000 100 * 50
9 ,,
_ 1250 (10) 25 43**
10' 2000 100 * 50
11 2' 1250 (10) 25 43**
12 7' 4000 100 * 50
Y..= 1 hour
* for expected range see appendix 06.5
= target only
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52
Performance determination:
The initial power PO,KC [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot. The procedure
is described in
Issue 5 of the test procedure (CEC F-98-08). This is done using the same test
setup and the
PEUGEOTTm DW10 engine type.
The final performance (Pend,KC) is determined in the 12th cycle in stage 12
(see table1 above,
figure 2). Here too, the operation point is full load 4000/min. Pend,KC [kW]
is calculated from
the torque measured.
The power loss in the KC test is calculated as follows:
Pend., K C
Power loss ,KC = (1 4, 10 0
PO, K C
2.2. DW10 dirty-up clean-up (DU-CU)
The DU-CU test is based on CEC test procedure F-098-08 Issue 5. The procedure
is described
in Issue 5 of the test procedure (CEC F-98-08). This is done using the same
test setup and the
PEUGEOT DW10 engine type.
The DU ¨ CU test consists of two individual tests which are run in succession.
The first test
serves to form deposits (DU), the second to remove the deposits (CU). After
the DU, the power
loss is determined. After the end of the DU run, the engine is not operated
for at least 8 hours
and is cooled to ambient temperature. Thereafter, the CU fuel is used to start
the CU without
deinstalling and cleaning the injectors. The deposits and power loss ideally
decline over the
course of the CU test.
Change and special features:
Cleaned injectors were installed in the engine prior to each DU test. The
cleaning time in the
ultrasound bath at 60 C, in water + 10% Superdecontamine (Intersciences,
Brussels), was 4
h.
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53
Test run times:
The test run time was 12 h for the DU and 12 h for the CU. The engine was
operated in the
DU and CU tests without shutdown phases.
The one-hour test cycle from CEC F-098-08, shown in figure 2, was run through
12 times in
each case.
Performance determination:
The initial power PO,du [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot. The procedure
is likewise
described in Issue 5 of the test procedure.
The final performance (Pend,du) is determined in the 12th cycle in stage 12
(see table above).
Here too, the operation point is full load 4000/min. Pend,du [kW] is
calculated from the torque
measured.
The power loss in the DU is calculated as follows:
Pend,du)
Power lossidu [541= (1 po,dU )* 100
Clean-up
The initial power PO,cu [kW] is calculated from the measured torque at full
load 4000/min
directly after the test has started and the engine has run hot in the CU. The
procedure is
likewise described in Issue 5 of the test procedure.
The final performance (Pend,cu) is determined in the 12th cycle in stage 12
(see table 1 above,
figure 2). Here too, the operation point is full load 4000/min. Pend,cu [kW]
is calculated from
the torque measured.
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The power loss in the CU test is calculated as follows (negative number for
the power loss in
the cu test means an increase in performance)
Power loss muumtsi = ( Pen d, du d,
* 100
PO, du
The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To
artificially
induce the formation of deposits at the injectors, 1 ppm by weight of zinc in
the form of a zinc
didodecanoate solution was added thereto.
3. IDID test ¨ determination of additive effect on internal injector
deposits
The formation of deposits within the injector was characterized by the
deviations in the
exhaust gas temperatures of the cylinders at the cylinder outlet on cold
starting of the DW10
engine.
To promote the formation of deposits, 1 mg/I of sodium salt of an organic
acid, 20 mg/I of
dodecenylsuccinic acid and 10 mg/I of water were added to the fuel.
The test is conducted as a dirty-up clean-up test (DU-CU).
DU-CU is based on CEC test procedure F-098-08 Issue 5.
The DU ¨ CU test consists of two individual tests which are run in succession.
The first test
serves to form deposits (DU), the second to remove the deposits (CU).
After the DU run, after a rest phase of at least eight hours, a cold start of
the engine is
conducted, followed by idling for 10 minutes.
Thereafter, the CU fuel is used to start the CU without deinstalling and
cleaning the injectors.
After the CU run over 8 h, after a rest phase of at least eight hours, a cold
start of the engine
is conducted, followed by idling for 10 minutes. The evaluation is effected by
the comparison
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of the temperature profiles for the individual cylinders after the cold start
in the du and CU
runs.
The IDID test indicates the formation of internal deposits in the injector.
The characteristic
5 used in this test is the exhaust gas temperature of the individual
cylinders. In an injector
system without IDIDs, the exhaust gas temperatures of the cylinders increase
homogeneously. In the presence of IDIDs, the exhaust gas temperatures of the
individual
cylinders do not increase homogeneously and deviate from one another.
10 The temperature sensors are beyond the cylinder head outlet in the
exhaust gas manifold.
Significant deviation of the individual cylinder temperatures (e.g. > 20 C)
indicates the
presence of internal injector deposits (IDIDs).
The tests (DU and CU) are each conducted with run time 8 h. The one-hour test
cycle from
15 CEC F-098-08 is run through 8 times in each case. In the event of
deviations of the individual
cylinder temperatures of greater than 45 C from the mean for all 4 cylinders,
the test is
stopped early.
25
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56
B. Preparation and analysis examples:
Reactants used:
N, N-dimethylethanolamine CAS. 108-01-0 from BASF
1,2-Propylene oxide CAS. 75-56-9 from BASF
1,2-Butylene oxide CAS. 106-88-7 from BASF
Potassium tert-butoxide CAS. 865-47-4 from Aldrich
Dimethyl oxalate CAS. 553-90-2 from Aldrich
Solvent Naphtha Heavy CAS. 64742-94-5 from Exxon Mobil
Styrene oxide CAS. 96-09-3 from Aldrich
2-Ethylhexanol CAS. 104-76-7 from BASF
Lauric acid CAS. 143-07-7 from Aldrich
lsotridecanol N CAS. 27458-92-0 from BASF
Acetic acid, pure CAS. 64-19-7 from Aldrich
Formic acid, 85% in H20 CAS 64-18-6 from Kraft
Formalin, 36.5% CAS 50-00-0 from Aldrich
Polydispersities D were determined by means of gel permeation chromatography.
Synthesis example 1: N,N-Dimethylethanolamine*15 PO (A)
In a 21 autoclave, N,N-dimethylethanolamine (76.7 g) is admixed with potassium
tert-
butoxide (4.1 g). The autoclave is purged three times with N2, a supply
pressure of approx.
1.3 bar of N2 is established and the temperature is increased to 130 C. 1,2-
Propylene oxide
(750 g) is metered in over a period of 10 h, in such a way that the
temperature remains
between 129 C-131 C. This is followed by stirring at 130 C for 6 h, purging
with N2, cooling
to 60 C and emptying of the reactor. Excess propylene oxide is removed under
reduced
pressure on a rotary evaporator. The basic crude product is neutralized with
the aid of
commercial magnesium silicates, which are subsequently filtered off. This
gives 831 g of the
product in the form of an orange oil (TBN 58.1 mg KOH/g; D 1.16).
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Synthesis example 2: N,N-Dimethylethanolamine*25 BuO (B)
In a 21 autoclave, N,N-dimethylethanolamine (47.1 g) is admixed with potassium
tert-
butoxide (5.0 g). The autoclave is purged three times with N2, a supply
pressure of approx.
1.3 bar of N2 is established and the temperature is increased to 140 C. 1,2-
Butylene oxide
(953 g) is metered in over a period of 9 h, in such a way that the temperature
remains
between 138 C-141 C. This is followed by stirring at 140 C for 6 h, purging
with N2, cooling
to 60 C and emptying of the reactor. Excess butylene oxide is removed under
reduced
pressure on a rotary evaporator. The basic crude product is neutralized with
the aid of
commercial magnesium silicates, which are subsequently filtered off. This
gives 1000 g of
the product in the form of a yellow oil (TBN 28.1 mg KOH/g; D 1.12).
Synthesis example 3: N,N-Dimethylethanolamine*15 PO quaternized with dimethyl
oxalate
(I)
Polyetheramine (A) (250 g) from Synthesis example 1 is admixed with dimethyl
oxalate
(59 g) and lauric acid (12.5 g) and the reaction mixture is stirred at a
temperature of 120 C
for 4 h. Subsequently, excess dimethyl oxalate is removed at a temperature of
120 C on a
rotary evaporator under reduced pressure (p = 5 mbar). This gives 290 g of the
product. 1H
NMR analysis of the quaternized polyetheramine thus obtained shows the
quaternization.
Synthesis example 4: N,N-Dimethylethanolamine*25 BuO quaternized with dimethyl
oxalate
(II)
Polyetheramine (B) (250 g) from Synthesis example 2 is admixed with dimethyl
oxalate
(67.3 g) and lauric acid (6.2 g) and the reaction mixture is stirred at a
temperature of 120 C
for 4.5 h. Subsequently, excess dimethyl oxalate is removed at a temperature
of 120 C on a
rotary evaporator under reduced pressure (p = 5 mbar). This gives 270 g of the
product. 1H
NMR analysis of the quaternized polyetheramine thus obtained shows the
quaternization.
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Synthesis example 5: N,N-Dimethylethanolamine*25 BuO quaternized with styrene
oxide/acetic acid (III)
Polyetheramine (B) (400 g) from Synthesis example 2 is dissolved in Solvent
Naphtha Heavy
(436 g), admixed with styrene oxide (24.0 g) and acetic acid (12.0 g), and
then stirred at a
temperature of 80 C for 8 h. After cooling to room temperature, 870 g of the
product are
obtained. 1H NMR analysis of the solution of the quaternized polyetheramine in
Solvent
Naphtha Heavy thus obtained shows the quaternization.
Synthesis example 6: N,N-Dimethylethanolamine*15 PO quaternized with propylene
oxide/acetic acid (IV)
In a 21 autoclave, polyetheramine (A) (305 g) from Synthesis example 1 is
dissolved in 2-
.. ethylhexanol (341 g) and admixed with acetic acid (18.3 g). The autoclave
is purged three
times with N2, a supply pressure of approx. 1.3 bar of N2 is established and
the temperature
is increased to 130 C. 1,2-Propylene oxide (17.7 g) is metered in. This is
followed by stirring
at 130 C for 5 h, purging with N2, cooling to 40 C and emptying of the
reactor. Excess
propylene oxide is removed on a rotary evaporator under reduced pressure. This
gives 675 g
.. of the product in the form of an orange oil. 1H NMR analysis of the
solution of the quaternized
polyetheramine in 2-ethylhexanol thus obtained shows the quaternization.
Synthesis example 7: N,N-Dimethylethanolamine*15 PO quaternized with ethylene
oxide/acetic acid (V)
In a 21 autoclave, polyetheramine (A) (518 g) from Synthesis example 1 is
dissolved in 2-
ethylhexanol (570 g) and admixed with conc. acetic acid (30 g). The autoclave
is purged
three times with N2, a supply pressure of approx. 1.3 bar of N2 is established
and the
temperature is increased to 130 C. Ethylene oxide (22 g) is metered in. This
is followed by
stirring at 130 C for 5 h, purging with N2, cooling to 40 C and emptying of
the reactor. This
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59
gives 1116 g of the product in the form of an orange oil. 1H NMR analysis of
the solution of
the quaternized polyetheramine in 2-ethylhexanol thus obtained shows the
quaternization.
Synthesis example 8: lsotridecanol N*22 BuO: polyether (C)
The polyether is prepared from isotridecanol N and 1,2-butylene oxide in a
molar ratio of 1:22
according to known processes, by DMC catalysis as described, for example, in
EP 1591466A.
Synthesis example 9: lsotridecanol (Tridecanol N, BASF)*22 BuO aminated with
NH3: prim.
polyetheramine (D)
The prim. polyetheramine (ID) is prepared by reaction of the polyether (C)
from Synthesis
example 8 with NH3 in the presence of a suitable hydrogenation catalyst
according to known
processes, as described, for example, in DE3826608A. The analysis of the
polyetheramine
(D) thus obtained gives TBN 32.0 mg KOH/g.
Synthesis example 10: tert-Polyetheramine (E)
The polyetheramine (D) (400 g) from Synthesis example 9 is admixed with formic
acid
(65.3 g, 85% in H20) while cooling with an ice bath. The reaction mixture is
subsequently
warmed up to a temperature of 45 C, and formaldehyde solution (44.9 g, 36.5%
in H20) is
added dropwise at this temperature, in the course of which the carbon dioxide
released is
drawn off from the reaction vessel. The reaction mixture is stirred at a
temperature of 80 C
for 16 h. Subsequently, the reaction mixture is cooled to room temperature,
admixed with
hydrochloric acid (37%; 35.4 g) and stirred at room temperature for 1 h. H20
(500 ml) is
added and the aqueous phase is adjusted to a pH of approx. 10 by adding 50%
potassium
hydroxide solution. Subsequently, the mixture is extracted repeatedly with
tert-butyl methyl
ether (1200 ml in total). The combined organic phases are washed with sat.
aqueous NaCI
solution and dried over MgSO4, and the solvent is removed under reduced
pressure. This
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gives 403 g of the product in the form of a yellow oil. 1H NMR analysis of the
tert-
polyetheramine thus obtained shows the reductive dimethylation.
Synthesis example 11: Isotridecanol (Tridecanol N, BASF)*22 BuO aminated with
NH3, red.
5 dimethylated, quaternized with dimethyl oxalate (VI)
tert-Polyetheramine (E) (172 g) from Synthesis example 10 is admixed with
dimethyl oxalate
(55.3 g) and lauric acid (5.2 g), and the reaction mixture is stirred at a
temperature of 120 C
for 4 h. Subsequently, excess dimethyl oxalate is removed on a rotary
evaporator under
10 reduced pressure (p = 5 mbar) at a temperature of 120 C. 1H NMR analysis
of the
quaternized polyetheramine thus obtained shows the quaternization.
Synthesis example 12: lsotridecanol (Tridecanol N, BASF)*22 BuO aminated with
NH3,
dimethylated, quaternized styrene oxide/acetic acid (VII)
tert-Polyetheramine (E) (200 g) from Synthesis example 10 is dissolved in
toluene (222 g),
admixed with styrene oxide (14.4 g) and conc. acetic acid (7.2 g), and then
stirred at a
temperature of 80 C for 7 h. 1H NMR analysis of the solution thus obtained
shows the
quaternization.
C. Use examples:
In the use examples which follow, the additives are used either as a pure
substance (as
synthesized in the above preparation examples) or in the form of an additive
package.
Use example 1: Determination of the additive action on the formation of
deposits in diesel
engine injection nozzles
a) XUD9 tests
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Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The results are compiled in Table 1.
Table 1: XUD9 tests
Ex. Designation Dosage according to Flow restriction
preparation example 0.1 mm needle
[mg of active stroke
ingredient/kg] [%]
#1 M1, according to 30 20.9
preparation example 4
#2 M2, according to 30 44.5
preparation example 3
b) DW10 test
The test results are shown in Table 2.
Table 2: Results of the DWI 0 tests
A Dose Power loss Power loss Power loss
dditive
[mg/kg] KC DU DU-CU
Base value 0 5.0%
M1, according to preparation
80 0.61%
example 6, keep-clean
M2, according to preparation 75 2.8% 1.7%
example 3, clean-up
Use example 2: Intake valve cleanliness (gasoline engine with suction tube
injection)
Method: MB M102 E (CEO F-05-93)
Fuel: E5 according to EN 228
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Additive according to Synthesis example 4
Results:
Intake valve deposits after end of test (mg/V)
Base value (no additive) 112
With 116 mg/kg of additive 86
Use example 3: Injector cleanliness
(Direct injection gasoline engine)
Method: BASF in-house method
Engine: turbocharged four-cylinder of capacity 1.6 liters
Test duration: 60 hours
Fuel: test fuel with 7% by volume of oxygen-containing components
Additives:
A: additive according to Synthesis example 4
B: additive according to Synthesis example 3
FR* FR* Injector appearance at end of
test
Start of test End of test
Base value (no 0.95 1.00 see fig. la
additive)
With 116 mg/kg 0.96 0.94 see fig. lb
of additive A
With 116 mg/kg 0.96 0.93 see fig. lc
of additive B
*: The FR is a parameter detected by the engine control, which correlates with
the duration of
the injection operation of the fuel into the combustion chamber. The more
marked is the
formation of deposits in the injector nozzles, the longer the injection time
and higher the FR.
63
Conversely, the FR remains constant or tends to decrease slightly when the
injector nozzles
remain free of deposits.
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