Note: Descriptions are shown in the official language in which they were submitted.
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Acid-free quatemised nitrogen compounds and use thereof as additives in fuels
and
lubricants
The present invention relates to novel acid-free quaternized nitrogen
compounds, to
the preparation thereof and to the use thereof as a fuel and lubricant
additive, more
particularly as a detergent additive, as a wax antisettling additive (WASA) or
as an
additive for reducing internal diesel injector deposits (IDID); to additive
packages which
comprise these compounds; and to fuels and lubricants thus additized. The
present
invention further relates to the use of these acid-free quatemized nitrogen
compounds
.. as a fuel additive for reducing or preventing deposits in the injection
systems of direct-
injection diesel engines, especially in common-rail injection systems, for
reducing the
fuel consumption of direct-injection diesel engines, especially of diesel
engines with
common-rail injection systems, and for minimizing power loss in direct-
injection diesel
engines, especially in diesel engines with common-rail injection systems.
State of the art:
In direct-injection diesel engines, the fuel is injected and distributed
ultrafinely
(nebulized) by a multihole injection nozzle which reaches directly into the
combustion
chamber 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.
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
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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 NO,.
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 (NOõ), carbon monoxide (CO) and especially of particulates
(soot). This
makes it possible, for example, that engines equipped with common-rail
injection
systems can meet the Euro 4 standard theoretically even without additional
particulate
filters.
In modern common-rail diesel engines, under particular conditions, for example
when
biodiesel-containing fuels or fuels with metal impurities such as zinc
compounds,
copper compounds, lead compounds and other metal compounds are used, deposits
can form on the injector orifices, which adversely affect the injection
performance of the
fuel and hence impair the performance of the engine, i.e. especially reduce
the power,
but in some cases also worsen the combustion. The formation of deposits is
enhanced
further by further developments in the injector construction, especially by
the change in
the geometry of the nozzles (narrower, conical orifices with rounded outlet).
For lasting
optimal functioning of engine and injectors, such deposits in the nozzle
orifices must be
prevented or reduced by suitable fuel additives.
WO 2006/135881 describes quaternized ammonium salts prepared by condensation
of
a hydrocarbyl-substituted acylating agent and of an oxygen- or nitrogen-
containing
compound with a tertiary amino group, and subsequent quaternization by means
of
hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid,
especially
acetic acid. Stoichiometric amounts of the acid are required to ensure
complete ring
opening of the epoxide quaternizing agent and hence very substantially
quantitative
quaternization. The reaction of a dicarboxylic acid-based acylating agent,
such as the
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P I BSA used in the examples therein, with an amine, such as
dimethylaminopropylamine (DMAPA), under condensation conditions, i.e.
elimination of
water, forms a DMAPA succinimide which is then quaternized with epoxide and
acid in
equimolar amounts in each case.
Following the technical teaching of WO 2006/135881, the presence of the
stoichiometric amounts of acid, which is additionally absolutely necessary to
balance
the charge for the quaternized imide detergent therein, is found to be
particularly
disadvantageous. In order to reduce the acid content of the imide therein, or
in order to
entirely remove acid, additional process measures would be required, which
would
make the preparation of the product more complex and hence would make it much
more expensive. The epoxide-quaternized imide prepared according to
WO 2006/135881 is therefore ¨ without further purification ¨ used in the form
of the
carboxylate salt as a fuel additive in the tests described in the application.
On the other hand, however, it is known that acids can cause corrosion
problems in
fuel additives (cf., for example, Sugiyama et al; SAE International, Technical
Paper,
Product Code: 2007-01-2027, Date Published: 2007-07-23). The epoxide-
quaternized
additive provided according to WO 2006/135881 is therefore afflicted with
significant
application risks a priori owing to the considerable corrosion risk which
exists.
Furthermore, the product has distinct disadvantages with regard to motor oil
compatibility and low-temperature properties.
In the injection systems of modern diesel engines, deposits cause significant
performance problems. It is common knowledge that such deposits in the spray
channels can lead to a decrease in the fuel flow and hence to power loss.
Deposits at
the injector tip, in contrast, impair the optimal formation of fuel spray mist
and, as a
result, cause worsened combustion and associated higher emissions and
increased
fuel consumption. In contrast to these conventional "external" deposition
phenomena,
"internal" deposits (referred to collectively as internal diesel injector
deposits (IDID)) in
particular parts of the injectors, such as at the nozzle needle, at the
control piston, at
the valve piston, at the valve seat, in the control unit and in the guides of
these
components, also increasingly cause performance problems. Conventional
additives
exhibit inadequate action against these IDIDs.
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It is therefore an object of the present invention to provide improved
quaternized fuel
additives, especially based on hydrocarbyl-substituted polycarboxylic
anhydrides,
which no longer have the disadvantages of the prior art mentioned.
Brief description of the invention:
It has now been found that, surprisingly, the above object is achieved by
providing an
addition process, performable under acid-free conditions, for preparing
epoxide-
quaternized nitrogen-containing additives based on hydrocarbyl-substituted
polycarboxylic anhydrides and compounds which have quaternizable amino groups
and are reactive therewith, and by the acid-free reaction products thus
obtainable.
The inventive reaction regime surprisingly allows the addition of free acid to
be
dispensed with completely, especially of free protic acid which, according to
the prior
.. art, necessarily has to be added to the alkylene oxide quaternizing
reagent. This is
because the inventive process regime, by virtue of addition of the nitrogen-
containing
quaternizable compound onto the hydrocarbyl-substituted polycarboxylic
anhydride and
opening of the anhydride ring, generates an intramolecularly bound acid
function, and it
is assumed that, without being bound to this model consideration, that this
intramolecularly generated carboxyl group activates the alkylene oxide in the
quaternization reaction and, by protonation of the intermediate alcohol which
forms
after the addition of the alkylene oxide, forms the reaction product in the
form of a
betaine structure.
Surprisingly, the inventive additives thus prepared are superior in several
respects to
the prior art additives prepared in a conventional manner by epoxide/acid
quatemization.
Description of figures:
Figure 1 shows the power loss of different diesel fuels in a DW10 engine test.
In
particular, this is shown for unadditized fuel (squares) and a fuel additized
in
accordance with the invention (rhombuses), compared to a comparative fuel
admixed
with prior art additive at the same dosage (triangles).
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Detailed description of the invention:
Al) Specific embodiments
5 The present invention relates especially to the following specific
embodiments:
1. A process for preparing quaternized nitrogen compounds, wherein
a. a compound comprising at least one oxygen- or nitrogen-containing group
reactive with the anhydride, for example an ¨OH and/or a primary or
secondary amino group, and additionally comprising at least one
quaternizable amino group is added onto a polycarboxylic anhydride
compound, especially a polycarboxylic anhydride or a hydrocarbyl-substituted
polycarboxylic anhydride, especially a polyalkylene-substituted polycarboxylic
anhydride, and
b. the product from stage a) is quaternized with an especially H-E donor-free
and
in particular acid-free quaternizing agent.
2. The process according to embodiment 1, wherein the polycarboxylic anhydride
compound is a di-, tri- or tetracarboxylic anhydride.
3. The process according to either of the preceding embodiments, wherein the
polycarboxylic anhydride compound is the anhydride of a C4-C10-dicarboxylic
acid.
4. The process according to any of the preceding embodiments, wherein the
polycarboxylic anhydride compound comprises at least one high molecular
weight hydrocarbyl substituent, especially polyalkylene substituent, having a
number-average molecular weight (Mn) in the range from about 200 to 10 000,
for example 300 to 8000, especially 350 to 5000.
5. The process according to any of the preceding embodiments, wherein the
compound reactive with the anhydride is selected from
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a. mono- or polyamines which are substituted by low molecular weight
hydroxyhydrocarbyl, especially low molecular weight hydroxyalkyl, and have
at least one quaternizable primary, secondary or tertiary amino group;
b. straight-chain or branched, cyclic, heterocyclic, aromatic or
nonaromatic
polyamines having at least one primary or secondary (anhydride-reactive)
amino group and having at least one quaternizable primary, secondary or
tertiary amino group;
c. piperazines.
6. The process according to embodiment 5, wherein the compound reactive with
the
anhydride is selected from
a. primary, secondary or tertiary monoamines substituted by low molecular
weight hydroxyhydrocarbyl, especially low molecular weight hydroxyalkyl,
and hydroxyalkyl-substituted primary, secondary or tertiary diamines,
b. straight-chain or branched aliphatic diamines having two primary amino
groups; di- or polyamines having at least one primary and at least one
secondary amino group; di- or polyamines having at least one primary and
at least one tertiary amino group; aromatic carbocyclic diamines having two
primary amino groups; aromatic heterocyclic polyamines having two primary
amino groups; aromatic or nonaromatic heterocycles having one primary
and one tertiary amino group.
7. The process according to any of the preceding embodiments, wherein the
quaternizing agent is selected from epoxides, especially hydrocarbyl-
substituted
epoxides.
8. The process according to embodiment 7, wherein the quaternization is
effected
without addition of an H+ donor, especially without addition of acid.
9. The process according to any of the preceding embodiments, wherein stage
a),
i.e. the addition reaction, is performed at a temperature of less than about
80 C
and especially at a temperature in the range from about 30 to 70 C, in
particular
to 60 C.
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10. The process according to any of the preceding embodiments, wherein
stage a) is
performed over a period of 1 minute to 10 hours or 10 minutes to 5 hours or 10
minutes to 4 hours or 2 to 3 hours.
11. The process according to any of the preceding embodiments, wherein stage
b),
i.e. the quaternization, is performed at a temperature in the range from 40 to
80 C.
12. The process according to any of the preceding embodiments, wherein
stage b) is
performed over a period of 1 to 10 hours.
13. The process according to any of the preceding embodiments, wherein
stage b) is
performed with an epoxide, especially low molecular weight hydrocarbyl
epoxide,
as the quaternizing agent in the absence of (stoichiometric amounts of) free
acid
(other than the polycarboxylic acid compound).
14. The process according to any of the preceding embodiments, wherein the
reaction according to stage a) and/or b) is effected in the absence of a
solvent, in
particular in the absence of an organic protic solvent.
15. A quaternized nitrogen compound or reaction product obtainable by a
process
according to any of the preceding embodiments.
16. A quaternized nitrogen compound or reaction product according to
embodiment
15, comprising at least one compound of the general formulae:
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p p I
ng-, 0 0
Lul
-6c --,NR4õ 0 0 R4
2
11 L
11 L y
Rr y Ri
0 R2 \ R3
0 R, R3
0 R1
R2
(12-1) (la-2) OyL,
RS-R6 0
I 4.
5,,N,. 0 0
Lc R4
114 L
R( y
0 R21 R3
0- Ri
0
R,
R I+
L2 R7
(la-3)
especially la-1, optionally in combination with la-2 and/or la-3,
or
R 2
p 1
-gs;"..N., 0 0
Lc
-5-3.N, 0 0- R,
R4
oyLi oyLi
Ri
0 R2 \ R3
0 Ri R3
0 R,
R2
(lb-1) (lb-2) 0y1-1
0
R
0 0-
L2 R4
1_1
6
1R,
R2 \ R3
0- Ri
0 L0
R4
0
R( 1-;
(Ib-3)
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especially lb-1, optionally in combination with lb-2 and/or lb-3,
in which
R1 is H or a straight-chain or branched hydrocarbyl radical which may
optionally
be mono- or polysubstituted by hydroxyl, carboxyl, hydrocarbyloxy and/or acyl
radicals, or has one or more ether groups in the hydrocarbyl chain, and is
especially H or short-chain hydrocarbyl, especially alkyl;
R2 is H or alkyl; R3 is hydrocarbyl, especially long-chain hydrocarbyl, for
example
a polyalkylene radical;
at least one of the R4, R5 and R6 radicals is a radical introduced by
quaternization, especially a low molecular weight hydrocarbyl radical or low
molecular weight hydroxyl-substituted hydrocarbyl radical, and the remaining
radicals are selected from straight-chain or branched low molecular weight
hydrocarbyl radicals, cyclic hydrocarbyl radicals, which are optionally mono-
or
polysubstituted and/or have one or more heteroatoms;
R7 is H or a straight-chain or branched low molecular weight hydrocarbyl
radical
which may optionally be mono- or polysubstituted, for example di-, tri- or
tetrasubstituted, by identical or different hydroxyl, carboxyl, low molecular
weight
hydrocarbyloxy and/or acyl radicals, or has one or more ether groups in the
hydrocarbyl chain, or R7 together with one of the R4, R5 and R6 radicals forms
a
bridge group, for example an alkylene or alkenylene group;
Li is a chemical bond or a straight-chain or branched alkylene group and
L2 is a straight-chain or branched alkylene group which optionally bears one
or
more heteroatoms, especially selected from ¨0- and ¨NH-, or substituents.
17. A quaternized nitrogen compound or reaction product according to
embodiment
15 or 16 which is essentially H4 donor-free, especially essentially acid-free,
and
especially comprises no inorganic acids or short-chain organic acids.
18. The use of a quaternized nitrogen compound or of a reaction product
according
to any of embodiments 15 to 17 as a fuel additive or lubricant additive.
19. The use according to embodiment 18 as a detergent additive for diesel
fuels.
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20. The use according to embodiment 18 as a wax antisettling additive (WASA)
for
middle distillate fuels, especially diesel fuels.
21. The use according to embodiment 19 as an additive for reducing or
preventing
5 deposits in
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/or for minimizing power loss in direct-injection diesel engines,
especially in diesel engines with common-rail injection systems.
22. The use according to embodiment 21 as an additive for controlling
(preventing or
reducing, especially partly, essentially completely or completely reducing)
internal diesel engine deposits (IDID), i.e. deposits in the interior of the
injector;
especially wax or soap-like deposits and/or carbon-like polymeric deposits.
23. An additive concentrate comprising, in combination with further fuel
additives,
especially diesel fuel additives, at least one quaternized nitrogen compound
or a
reaction product according to either of embodiments 15 and 16.
24. A fuel composition comprising, in a majority of a customary base fuel, a
(detergency-)effective amount of at least one quaternized nitrogen compound or
of a reaction product according to either of embodiments 15 and 16.
25. A lubricant composition comprising, in a majority of a customary
lubricant, a
(detergency-)effective amount of at least one quaternized nitrogen compound or
of a reaction product according to either of embodiments 15 and 16.
A2) General definitions
An "H+ donor" or "proton donor" refers to any chemical compound which is
capable of
releasing a proton to a proton acceptor. Examples are especially protic acids,
but also
water.
"Acid-free" in the context of the present invention means the absence of low
molecular
weight inorganic or organic acid and/or of the corresponding anion thereof,
and
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includes both the lack of addition of acid during the preparation process
according to
the invention and, more particularly, the absence of acid and/or of the anion
thereof in
the quaternized reaction product used as the additive. Freedom from acid
includes
especially the absence of stoichiometric amounts of such acids and anions
thereof
(stoichiometry based on the quaternizing agent used, such as especially the
epoxide),
and exists especially when, based on epoxide quaternizing agent used, free
acid or
anion thereof is present only in substoichiometric amounts, 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
quaternizing agent to
acid. Freedom from acid especially also includes the complete absence of an
inorganic
or organic protic acid and/or anion thereof (i.e. when protic acid and/or the
anion
thereof is analytically no longer detectable). An "acid" in this context is
especially a free
protic acid.
Examples of typical "protic acids" include inorganic acids or mineral acids,
such as HCI,
H2SO4, HNO3, H2CO3, and organic carboxylic acids, especially monocarboxylic
acids of
the RCOOH type in which R is a short-chain hydrocarbyl radical.
"Free" or "unbound" acid means that the acid function is not part of a
quaternized
compound itself, i.e. is in principle removable from the quaternized compound,
for
= 20 example by ion exchange.
Typical "anions" of protic acids are, for example, carboxylate anions, for
example
acetate and propionate.
"Quaternizable" nitrogen groups or amino groups include especially primary,
secondary
and tertiary amino groups.
A "condensation" or "condensation reaction" in the context of the present
invention
describes the reaction of two molecules with elimination of a relatively small
molecule,
especially of a water molecule. When such an elimination is not detectable,
more
particularly not detectable in stoichiometric amounts, and the two molecules
react
nevertheless, for example with addition, the reaction in question of the two
molecules is
"without condensation".
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A "betaine" refers to a specific salt form of a chemical compound which has
both a
negative charge and a positive charge in one and the same molecule, wherein
the
charge, however, cannot be eliminated by intramolecular ion transfer.
"IDID" stands for "internal diesel injector deposits", as observed in modern
diesel
engines. While conventional (external) deposits are coke-like deposits in the
region of
the needle tips and the spray holes of the injection nozzles, there is in the
meantime an
accumulation of deposits in the interior of the injection nozzles, which lead
to significant
performance problems, for example blockage of the internal moving parts of the
valve
and associated worsening or lack of control of fuel injection, power loss and
the like.
The IDIDs occur either in the form of wax- or soap-like deposits (fatty acid
residues
and/or C12- or C16-alkyl succinic acid residues detectable analytically) or in
the form of
polymeric carbon deposits. The latter in particular make particular demands
with regard
to the removal/avoidance thereof.
In the absence of statements to the contrary, the following general conditions
apply:
"Hydrocarbyl" can be interpreted widely and comprises both long-chain and
short-
chain, straight-chain and branched hydrocarbon radicals, which may optionally
additionally comprise heteroatoms, for example 0, N, NH, S, in the chain
thereof.
"Cyclic hydrocarbyl radicals" may comprise aromatic or nonaromatic rings and
optionally have one or more ring heteroatoms selected from 0, S, N, NH.
.. "Long-chain" or "high molecular weight" hydrocarbyl radicals have a number-
average
molecular weight (Mr,) of 85 to 20 000, for example 113 to 10 000, or 200 to
10 000 or
350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to
1500. More
particularly, they are formed essentially from C2-6, especially C2-4, monomer
units such
as ethylene, propylene, n- or isobutylene or mixtures thereof, where the
different
monomers may be copolymerized in random distribution or as blocks. Such long-
chain
hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C2-
6- or poly-
C2_4-alkylene radicals. Suitable long-chain hydrocarbyl radicals and the
preparation
thereof are also described, for example, in WO 2006/135881 and the literature
cited
therein.
13
Examples of particularly useful polyalkylene radicals are polyisobutenyl
radicals
derived from "high-reactivity" polyisobutenes which are notable for a high
content of
terminal double bonds. Terminal double bonds are alpha-olefinic double bonds
of the
type
Polymer _______________________________
which are also referred to collectively as vinylidene double bonds. Suitable
high-
reactivity polyisobutenes are, for example, polyisobutenes which have a
proportion of
vinylidene double bonds of greater than 70 nnol%, especially greater than 80
mol /0 or
greater than 85 mol%. Preference is given especially to polyisobutenes which
have
homogeneous polymer structures. Homogeneous polymer structures are possessed
especially by those polyisobutenes formed from isobutene units to an extent of
at least
85% by weight, preferably to an extent of at least 90% by weight and more
preferably
to an extent of at least 95% by weight. Such high-reactivity polyisobutenes
preferably
have a number-average molecular weight within the abovementioned range. In
addition, the high-reactivity polyisobutenes may have a polydispersity in the
range from
1.05 to 7, especially of about 1.1 to 2.5, for example of less than 1.9 or
less than 1.5.
Polydispersity is understood to mean the quotient of weight-average molecular
weight
Mw divided by the number-average molecular weight Mn.
Particularly suitable high-reactivity polyisobutenes are, for example, the
GlissopalTM
brands from BASF SE, especially GlissopalTM 1000 (Mn = 1000), GlissopalTM V33
(Mn = 550) and GlissopalTM 2300 (Mn = 2300), and mixtures thereof. Other
number-
average molecular weights can be established in a manner known in principle by
mixing polyisobutenes of different number-average molecular weights or by
extractive
enrichment of polyisobutenes of particular molecular weight ranges.
"Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" is especially
straight-
chain or branched alkyl or alkenyl, optionally interrupted by one or more, for
example 2,
3 or 4, heteroatom groups such as -0- or ¨NH-, or optionally mono- or
polysubstituted,
for example di-, tri- or tetrasubstituted.
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14
"Short-chain hydrocarbyloxy" or "low molecular weight hydrocarbyloxy" is
especially
straight-chain or branched alkyloxy or alkenyloxy, optionally interrupted by
one or
more, for example 2, 3 or 4, heteroatom groups such as -0- or -NH-, or
optionally
mono- or polysubstituted, for example di-, tri- or tetrasubstituted.
"Hydroxyl-substituted ,hydrocarbyl" or "hydroxyhydrocarbyl" represents
especially the
hydroxyl-substituted analogs of the alkyl or alkenyl radicals defined herein.
"Alkyl" or "lower alkyl" represents especially saturated, straight-chain or
branched
hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20,
carbon atoms,
for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-
methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-
methylbutyl,
2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-
dimethylpropyl, 1-
methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-
dimethylbutyl, 1,2-
dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-
dimethylbutyl,
1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-
ethy1-1-
methylpropyl and 1-ethyl-2-methylpropyl; and also n-heptyl, n-octyl, n-nonyl
and n-
decyl, and the singly or multiply branched analogs thereof.
"Hydroxyalkyl" represents especially the mono- or polyhydroxylated, especially
monohydroxylated, analogs of the above alkyl radicals, for example the
monohydroxylated analogs of the above straight-chain or branched alkyl
radicals, for
example the linear hydroxyalkyl groups with a primary hydroxyl group, such as
hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.
"Alkenyl" represents mono- or polyunsaturated, especially monounsaturated,
straight-
chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10
or 2 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-
methy1-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,
1-methyl-
3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-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-
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pentenyl, 3-methyl-1-pentenyl, 4-methy1-1-pentenyl, 1-methyl-2-pentenyl, 2-
methy1-2-
pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-
methy1-3-
pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-
methy1-4-
pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-
pentenyl, 1,1-dimethy1-2-butenyl,
5 1,1-dinnethy1-3-
butenyl, 1,2-dimethy1-1-butenyl, 1,2-dimethy1-2-butenyl, 1,2-dimethy1-3-
butenyl, 1,3-dinnethy1-1-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-ethy1-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-
butenyl, 1,1,2-
10 trimethy1-2-p
rope nyl, 1-ethyl-1-methy1-2-propenyl, 1-ethyl-2-methyl-1-propenyl and
1-ethyl-2-methyl-2-propenyl.
"Hydroxyalkenyl" represents especially the mono- or polyhydroxylated,
especially
monohydroxylated, analogs of the above alkenyl radicals.
"Alkyloxy" and "alkenyloxy" represent especially the oxygen-bonded analogs of
the
above "alkyl" and "alkenyl" radicals.
"Alkylene" represents straight-chain or mono- or polybranched hydrocarbon
bridge
groups having 1 to 10 carbon atoms, for example C1-07-alkylene 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 Ci-C4-alkylene groups selected from -CH2-, -(CH2)2-, -(CH2)3-, -
(CH2)4-,
-(CH2)2-CH(CH3)-, -CH2-CH(CH3)-CH2-;
or represents C2-C6-alkylene groups, for example CH2-CH(CH3)-, -CH(CH3)-CH2-,
-CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CI-12-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-propyl)-, -CH(n-propyI)-CH2-,
-CH(n-propyI)-CH(CH3)-, -CH2-CH(n-butyl)-, -CH(n-
butyl)-CH2-, -CH(CH3)-
CH(CH2CH3)-, -CH(CH3)-CH(n-propyI)-, -CH(CH2CH3)-CH(CH3)-, -CH(CH3)-
CH(CH2CH3)-, or represents C2-C4-alkylene groups, for example selected from -
(CH2)2-
, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, -CHrC(CH3)r,
-
CH2-CH(CH2CH3)-, -CH(CH2CH3)-CH2-,
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"Alkenylene" represents the mono- or polyunsaturated, especially
monounsaturated,
analogs of the above alkylene groups having 2 to 10 carbon atoms, especially
C2-C7-
alkenylenes or C2-C4-alkenylenes, such as -CH=CH-, -CH=CH-CH2-, -CH2-CH=CH-,
-CH=CH-CH2-CH2-, -CH2-CH=CH-CH2-, -CH2-CH2-CH=CH-, -CH(CH3)-CH=CH-,
-CH2-C(CH3)=CH-.
"Acyl" represents radicals derived from straight-chain or branched, optionally
mono- or
polyunsaturated, optionally substituted Cl-C24, especially Ci-C12 or C1-C8,
monocarboxylic acids. For example, useful acyl radicals are derived from the
following
carboxylic acids: saturated acids such as formic acid, acetic acid, propionic
acid and n-
and i-butyric acid, n- and i-valeric acid, caproic acid, enanthic acid,
caprylic acid,
pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid,
myristic
acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid,
nonadecanoic acid,
arachic acid, behenic acid, lignoceric acid, cerotic acid and melissic acid;
monounsaturated acids such as acrylic acid, crotonic acid, palmitoleic acid,
oleic acid
and erucic acid; and diunsaturated acids such as sorbic acid and linoleic
acid. When
double bonds are present in the fatty acids, they may either be in cis form or
in trans
form.
"Cyclic hydrocarbyl radicals" comprise especially:
- cycloalkyl: carbocyclic radicals having 3 to 20 carbon atoms, for
example C3-C12-
cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference
is given
to cyclopentyl, cyclohexyl, cycloheptyl, and also to cyclopropylmethyl,
cyclopropylethyl,
cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl,
cyclohexylmethyl, or C3-C7-cycloalkyl such as cyclopropyl, cyclobutyl,
cyclopentyl,
cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclopropylethyl,
cyclobutylmethyl,
cyclopentylethyl, cyclohexylmethyl, where the bond to the rest of the molecule
may be
via any suitable carbon atom.
- cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having 5 to
8,
preferably up to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-
3-yl,
cyclohexen-1-yl, cyclohexen-3-y1 and cyclohexen-4-y1;
- aryl: mono- or polycyclic, preferably mono- or bicyclic, optionally
substituted
aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for
example
phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl,
fluorenyl,
CA 02804322 2013-01-03
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indenyl and phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4,
5 or 6
identical or different substituents.
- arylalkyl: the aryl-substituted analogs of the above alkyl radicals,
where aryl is
likewise as defined above, for example phenyl-C1-C4-alkyl radicals selected
from
phenylmethyl and phenylethyl.
- heterocyclyl: five- to seven-membered saturated, partially unsaturated
or
aromatic (= heteroaryl or hetaryl) heterocycles or heterocyclyl radicals
comprising one,
two, three or four heteroatoms from the group of 0, N and S. For example, the
following subgroups may be mentioned:
- 5- or 6-
membered saturated or monounsaturated heterocyclyl comprising
one or two nitrogen atoms and/or one oxygen or sulfur atom or one or two
oxygen and/or sulfur atoms as ring members, for example 2-tetrahydrofuranyl, 3-
tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-
pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-
isoxazolidinyl, 3-
isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-
pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-
oxazolidinyl,
2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-
imidazolidinyl,
2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 1-
piperidinyl,
2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-
tetrahydropyranyl,
4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-
hexahydropyridazinyl,
4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-
hexahydropyrimidinyl,
5-hexahydropyrimidinyl and 2-piperazinyl;
- 5-membered aromatic
heterocyclyl comprising, as well as carbon atoms,
one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur
or
oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-
thienyl,
2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-
oxazolyl,
5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,
and
1,3,4-triazol-2-y1;
- 5-membered
aromatic heterocyclyl which has 1, 2, 3 or 4 nitrogen atoms as
ring members, such as 1-, 2- or 3-pyrrolyl, 1-, 3- or 4-pyrazolyl, 1-, 2- or 4-
imidazolyl, 1,2,3-[1F1]-triazol-1-yl, 1,2,342FIFtriazol-2-yl, 1,2,3-[1F11-
triazol-4-yl,
1,2,342FIFtriazol-4-yl, 1,2,4-[11-11-triazol-1-yl,
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1,2,4-[1H]-triazol-5-yl, 1,2,4441-1]-
triazol-4-yl,
1,2,444Hpriazol-3-yl, OFIFtetrazol-1-yl, [1HI-tetrazol-5-yl, [2H]tetrazol-2-y1
and
[211]-tetrazol-5-y1;
- 5-membered aromatic
heterocyclyl which has 1 heteroatom selected from
oxygen and sulfur and optionally 1, 2 or 3 nitrogen atoms as ring members, for
example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3- or 4-isoxazolyl, 3- or 4-
isothiazolyl,
2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 1,2,4-thiadiazol-3-yl, 1,2,4-
thiadiazol-5-
yl, 1,3,4-thiadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-y1 and
1,3,4-
oxadiazol-2-y1;
- 6-membered
heterocyclyl comprising, as well as carbon atoms, one or two,
or one, two or three, nitrogen atoms as ring members, for example 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-
pyrimidinyl,
5-pyrimidinyl, 2-pyrazinyl, 1,2,4-triazin-3-y1; 1,2,4-triazin-5-yl, 1,2,4-
triazin-6-y1
and 1,3,5-triazin-2-yl.
"Substituents" for radicals specified herein are especially selected from keto
groups,
-COOH, -COO-alkyl, ¨OH, -SH, -CN, amino, -NO2, alkyl, or alkenyl groups.
A3) Polycarboxylic anhydride compounds, such as especially polycarboxylic
anhydrides and hydrocarbyl-substituted polycarboxylic anhydrides:
The anhydride used is derived from any aliphatic di- or polybasic (for example
tri- or
tetrabasic), especially from di-, tri- or tetracarboxylic acids, and is
optionally substituted
by one or more (for example 2 or 3), especially a long-chain alkyl radical
and/or a high
molecular weight hydrocarbyl radical, especially a polyalkylene radical.
Examples are
anhydrides of C3¨C10 polycarboxylic acids, such as the dicarboxylic acids
malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic
acid and
sebacic acid, and the branched analogs thereof; and the tricarboxylic acid
citric acid.
The anhydrides can also be obtained from the corresponding monounsaturated
acids
and addition of at least one long-chain alkyl radical and/or high molecular
weight
hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric
acid,
maleic acid, itaconic acid.
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The hydrophobic "long-chain" or "high molecular weight" hydrocarbyl radical
which
ensures sufficient solubility of the quaternized product in the fuel has a
number-
average molecular weight (M.) of 85 to 20000, for example 113 to 10000, or 200
to
000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800
to
5 1500. Typical hydrophobic hydrocarbyl radicals include polypropenyl,
polybutenyl and
polyisobutenyl radicals, for example with a number-average molecular weight M.
of
3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500.
Suitable hydrocarbyl-substituted anhydrides are described, for example, in
10 DE 43 19 672 and WO 2008/138836.
Suitable hydrocarbyl-substituted polycarboxylic anhydrides also comprise
polymeric,
especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic
anhydrides.
Dimeric forms comprise especially two acid anhydride groups which can be
reacted
independently with the quaternizable nitrogen compound in the preparation
process
according to the invention.
A4) Quatemizing agents:
.. Useful quaternizing agents are in principle all compounds suitable as such.
In a
particular embodiment, however, the at least one quaternizable tertiary
nitrogen atom is
quaternized with at least one quaternizing agent selected from epoxides,
especially
hydrocarbyl epoxides:
a a
a 0 R
(II)
in which the Ra radicals present therein are the same or different and are
each H or a
hydrocarbyl radical, where the hydrocarbyl radical has at least Ito 10 carbon
atoms. In
particular, these are aliphatic or aromatic radicals, for example linear or
branched C1_10-
alkyl radicals, or aromatic radicals, such as phenyl or C14-alkylphenyl.
Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic
alkylene oxides,
such as especially C2-12-alkylene oxides, such as ethylene oxide, propylene
oxide, 1,2-
butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene
oxide), 1,2-
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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; and also aromatic-substituted
ethylene
5 oxides, such as optionally substituted styrene oxide, especially styrene
oxide or 4-
methylstyrene oxide.
In the case of use of epoxides as quaternizing agents, they are used
especially in the
absence of free acids, especially in the absence of free protic acids, such as
in
10 particular of 01_12-monocarboxylic acids such as formic acid, acetic
acid or propionic
acid, or C2.12-dicarboxylic acids such as oxalic acid or adipic acid; or else
in the
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 "acid-free" in the context of the present
invention.
A5) Quatemized or quatemizable nitrogen compounds:
The quaternizable nitrogen compound reactive with the anhydride is selected
from
a. hydroxyalkyl-substituted mono- or polyamines having at least one
quaternized
(e.g. choline) or quaternizable primary, secondary or tertiary amino group;
b. straight-chain or branched, cyclic, heterocyclic, aromatic or
nonaromatic
polyamines having at least one primary or secondary (anhydride-reactive) amino
group and having at least one quaternized or quaternizable primary, secondary
or tertiary amino group;
c. piperazines.
The quaternizable nitrogen compound is especially selected from
a. hydroxyalkyl-substituted primary, secondary, tertiary or quaternary
monoamines
and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary
diamines;
b. straight-chain or branched aliphatic diamines having two primary amino
groups;
di- or polyamines having at least one primary and at least one secondary amino
group; di- or polyamines having at least one primary and at least one tertiary
amino group; di- or polyamines having at least one primary and at least one
quaternary amino group; aromatic carbocyclic diamines having two primary
amino groups; aromatic heterocyclic polyamines having two primary amino
CA 02804322 2013-01-03
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groups; aromatic or nonaromatic heterocycles having one primary and one
tertiary amino group.
Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those
provided with at least one hydroxyalkyl substituent, for example 1, 2, 3, 4, 5
or 6
hydroxyalkyl substituents.
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.
Hydroxyallwl 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)alkylene-
diamines, 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.
Suitable "diamines" are alkylenediamines, and the N-alkyl-substituted analogs
thereof,
such as N-monoalkylated alkylenediamines and the N,N- or N,N'-dialkylated
alkylenediamines. Alkylene is especially straight-chain or branched C1-7- or
C1-4-
alkylene as defined above. Alkyl is especially Ci_ealkyl as defined above.
Examples
are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-
propylenediamine, 1,4-
butylenelediamine and isomers thereof, pentanediamine and isomers thereof,
hexanediamine and isomers thereof, heptanediamine and isomers thereof, and
also
mono- or di-alkylated, such as, for example, mono- or di-C1-C4-alkylated, such
as
methylated, for example, derivatives of the aforementioned diamine compounds,
such
as, for example, 3-dimethylamino-1-propylamine (DMAPA), N,N-diethyl-
aminopropylamine, and N,N-dimethylaminoethylamine.
Suitable straight-chain "polyamines" are, for example, dialkylenetriamine,
trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-
alkyl-
substituted analogs thereof, such as N-monoalkylated and the N,N- or N,N'-
dialkylated
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alkylenepolyamines. Alkylene is especially straight-chain or branched C1-7¨ or
C1-4-
alkylene as defined above. Alkyl is especially C1_4-alkyl as defined above.
Examples are especially diethylenetriamine,
triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine,
dipropylenetriamine,
tripropylenetetramine, tetrapropylenepentamine,
pentapropylenehexamine,
dibutylenetriamine, tributylenetetramine,
tetrabutylenepentamine,
pentabutylenehexamine; and the N,N-dialkyl derivatives thereof, especially the
N,N-di-
C1_4-alkyl derivatives thereof. Examples include: N,N-
dimethyldimethylenetriamine,
N,N-diethyldimethylenetriamine, N,N-
dipropyldimethylenetriamine, N,N-
dimethyldiethylene-1,2-triamine, N,N-diethyldiethylene-1,2-triamine, N,N-
dipropyldiethylene-1,2-triamine, N,N-dimethyldipropylene-1,3-triamine (i.e.
DMAPAPA),
N,N-diethyldipropylene-1,3-triamine, N,N-
dipropyldipropylene-1,3-triamine, N,N-
dimethyldibutylene-1,4-triamine, N,N-diethyldibutylene-1,4-triamine, N,N-
dipropyldibutylene-1,4-triamine, N,N-dinnethyldipentylene-1,5-triamine, N,N-
diethyldipentylene-1,5-triamine, N,N-
dipropyldipentylene-1,5-triamine, .. N,N-
dimethyldihexylene-1,6-triamine, N,N-diethyldihexylene-1,6-triamine and N,N-
dipropyldihexylene-1,6-triamine.
"Aromatic carbocyclic diamines" having two primary amino groups are the
diamino-
substituted derivatives of benzene, biphenyl, naphthalene,
tetrahydronaphthalene,
fluorene, indene and phenanthrene.
"Aromatic or nonaromatic heterocyclic polyamines" having two primary amino
groups
are the derivatives, substituted by two amino groups, of the following
heterocycles:
5- or 6-membered, saturated or monounsaturated heterocycles comprising one to
two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen
and/or
sulfur atoms as ring members, for example tetrahydrofuran, pyrrolidine,
isoxazolidine,
isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine,
pyrroline,
piperidine, piperidinyl, 1,3¨dioxane, tetrahydropyran, hexahydropyridazine,
hexahydropyrimidine, piperazine;
- 5-membered
aromatic heterocycles comprising, in addition to carbon atoms, two
or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen
atom as
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ring members, for example furan, thiane, pyrrole, pyrazole, oxazole, thiazole,
imidazole
and 1,3,4-triazole; isoxazole, isothiazole, thiadiazole, oxadiazole;
- 6-membered heterocycles comprising, in addition to carbon atoms, one
or two, or
one, two or three, nitrogen atoms as ring members, for example pyridinyl,
pyridazine,
pyrimidine, pyrazinyl, 1,2,4-triazine, 1,3,5-triazin-2-yl.
"Aromatic or nonaromatic heterocycles having one primary and one tertiary
amino
group" are, for example, the abovementioned N-heterocycles which are
aminoalkylated
on at least one ring nitrogen atom, and especially bear an amino-C1-4-alkyl
group.
"Aromatic or nonaromatic heterocycles having a tertiary amino group and a
hydroxyalkyl group" are, for example, the abovementioned N-heterocycles which
are
hydroxyalkylated on at least one ring nitrogen atom, and especially bear a
hydroxy-C1.
4-alkyl group.
Mention should be made especially of the following groups of individual
classes of
quatemizable nitrogen compounds:
,
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24
Group 1:
NAME FORMULA
Diamines with primary second nitrogen atom
Ethylenediamine NH2
NH2
1,2-Propylenediamine
1 ,3-Propylenediamine
HN NH
Isomeric butylenediamines, for example
1,5-Pentylenediamine H2NNH2
Isomeric pentanediamines, for example NH2
H2NNH2
Isomeric hexanediamines, for example
H2N,NH2
Isomeric heptanediamines, for example
Di- and polyamines with a secondary second nitrogen atom
N.NH2
Diethylenetriamine (DETA)
Dipropylenetriamine (DPTA), 3,3--
iminobis(N,N-dimethylpropylamine)
Triethylenetetramine (TETA)NH2
C
N H2 H2 N,,,1
Tetraethylenepentamine (TEPA)
H2N
(NH2 HN
Pentaethylenehexamine
LNNN)
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N-Methyl-3-amino-1-propylamine N N H
/ 2
CNINH2
Bishexamethylenetriamine
NH2
Aromatics
H2N
Diaminobenzenes, for example
H2N
H2N
Diaminopyridines, for example
Group 2:
NAME FORMULA
Heterocycles
1-(3-Aminopropyl)imidazole H2N
LJN
4-(3-Aminopropyl)morpholine
( \N-r-NH2
1 -(2-Ami noethylpi pe rid ine)
NH
2
2-(1-Piperazinyl)ethylamine (AEP) N N
N-Methylpiperazine 11¨\¨
Amines with a tertiary second nitrogen atom
H
2
3,3-Diamino-N-methyldipropylamine
NH2
3-Dimethylamino-1-propylamine (DMAPA) 2 11J
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26
N,N-Diethylaminopropylamine H2NNJ
N,N-Dimethylaminoethylamine
Group 3:
NAME FORMULA
Alcohols with a primary and secondary amine
Ethanolamine
OH
3-Hydroxy-1-propylamine I-12N'-"OH
HONIDiethanolamine
OH
I
HON
Diisopropanolamine
OH
N-(2-Hydroxyethyl)ethylenediamine /-1 ¨\¨NH2
HO
Alcohols with a tertiary amine
OH
Triethanolamine, (2,21,2"-Nitrilotriethanol)
HO
OH
HON
1-(3-Hydroxypropyl)imidazole
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27
HO /¨OH
Tris(hydroxymethyl)amine \--N
"¨OH
3-Dimethylamino-1-propanol
3-Diethylamino-1-propanol HO
...,-
2-Dimethylamino-1-ethanol
4-Diethylamino-1-butanol
A6) Preparation of inventive additives:
a) Amine addition and alcohol addition
The hydrocarbyl-substituted polycarboxylic anhydride compound is reacted with
the
quaternizable nitrogen compound under thermally controlled conditions, such
that there
is essentially no condensation reaction. More particularly, in accordance with
the
invention, no formation of water of reaction is observed. More particularly,
the reaction
is effected at a temperature in the range from 10 to 80 C, especially 20 to 60
C or 30
to 50 C. The reaction time may be in the range from a few minutes or a few
hours, for
example about 1 minute up to about 10 hours. The reaction can be effected at a
pressure of about 0.1 to 2 atm, but especially at approximately standard
pressure. In
particular, an inert gas atmosphere, for example nitrogen, is appropriate.
The reactants are initially charged especially in about equimolar amounts;
optionally, a
small molar excess of the anhydride, for example a 0.05- to 0.5-fold, for
example a 0.1-
to 0.3-fold, excess, is desirable. If required, the reactants can be initially
charged in a
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28
suitable inert organic aliphatic or aromatic solvent or a mixture thereof.
Typical
examples are, for example, solvents of the Solvesso series, toluene or xylene.
However, in another particular embodiment, the reaction is effected in the
absence of
organic solvents, especially protic solvents.
In the case of inventive performance of the reaction, the anhydride ring is
opened with
addition of the quatemizable nitrogen compound via the reactive oxygen or
nitrogen
group thereof (for example hydroxyl group or primary or secondary amine
group), and
without the elimination of water of condensation. The reaction product
obtained
comprises a polycarboxylic intermediate with at least one newly formed acid
amide
group or ester group and at least one intramolecular, bound, newly formed
carboxylic
acid or carboxylate group, in a stoichiometric proportion relative to the
quaternizable
amino group bound intrannolecularly by the addition reaction.
The reaction product thus formed can theoretically be purified further, or the
solvent
can be removed. Usually, however, this is not absolutely necessary, such that
the
reaction step can be transferred without further purification into the next
synthesis step,
the quaternization.
b) Quaternization
The epoxide-based quaternization in reaction step (b) is then carried out
without
addition of acid, in a complete renunciation of prior art methods described to
date. The
carboxyl radical formed by amine addition promotes the epoxide ring opening
and
hence the quaternization of the amino group. The reaction product obtained
therefore
does not have a free acid anion. Nevertheless, the product is uncharged owing
to its
betaine structure.
To perform the quaternization, the reaction product or reaction mixture from
stage a) is
admixed with at least one epoxide compound of the above formula (II),
especially in the
stoichiometric amounts required to achieve the desired quaternization. It is
possible to
use, for example, 0.1 to 1.5 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
CA 02804322 2013-01-03
29
tertiary amine group. Correspondingly higher use amounts are required to
quaternize a
secondary or primary amine group.
Typical working temperatures here are in the range from 15 to 90 C, especially
from 20
to 80 C or 30 to 70 C. The reaction time may be in the range of a few minutes
or a few
hours, for example about 10 minutes up to about 24 hours. The reaction can be
effected at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3
bar, but
especially at about standard pressure. 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 inert
organic aliphatic or aromatic solvent or a mixture thereof, or a sufficient
proportion of
solvent from reaction step a) is still present. Typical examples are, for
example,
solvents of the Solvesso series, toluene or xylene. In a further particular
embodiment,
the reaction, however, is performed in the absence of organic solvents,
especially
protic (organic) solvents.
"Protic solvents", which are especially not used in accordance with the
invention, are
especially those with a dielectric constant of greater than 9. Such protic
solvents
usually comprise at least one HO group and may additionally contain water.
Typical
examples are, for example, glycols and glycol ethers, and alcohols such as
aliphatic,
cyclic-aliphatic, aromatic or heterocyclic alcohols.
c) Workup of the reaction mixture
The reaction end product thus formed can theoretically be purified further, or
the
solvent can be removed. Usually, however, this is not absolutely necessary,
and so the
reaction product is usable without further purification as an additive,
optionally after
blending with further additive components (see below), especially since there
are of
course also no corrosive free protic acids present in the reaction product.
d) General example
As a nonlimiting example of the reaction of a polyalkylene-substituted
dicarboxylic
anhydride compound by amine addition or alcohol addition and subsequent
CA 02804322 2013-01-03
quaternization, reference is made to the following illustrative reaction
schemes in which
Ri to R7, L1 and L2 are each as defined above:
Stage 1: Preparation of the substituted dicarboxylic anhydride
0 0 0
0 0 0
free-radical or ,, j. L,
_...,..._
L + via ene reaction Ll
+ RR21 ...,, R3
Li y ''
R1 ,,R3 0 Ri
R1 R2 =..,
1-2 mol. eq. 1 mol. eq. R2 OIL1
0
5 (A) (B)
Stage 2a: Amination and quaternization
R
(3(3
0 R-- I
0 0-
Li" Ra,
L
Ri y 1
0 Ri R3
R2 R2
(A) (la-1)
R R
0 0 0 R---- I
5 N., 0 0- 0
R5--",N1 .!. 0-
' L.-, R4 L R4
2 2
Li 11 L 11 L1
R, R( y 1
R, R- y R,
7
IR, = -.... R3 ¨... ,- 0 R2' \ R3+ 0 R2 ' s\. R,
0 R, 0 Ri 0 Ri
0õ,,,,L, 0.,õ.,1, 0 RLiy0
II ii 11
0 o . p i."--N,õ ,N,
FV L R
10 (B) (la-2) (la-3) 5 2 7
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,
31
Stage 2b: Ester formation and quaternization
R
L.- R4IX 2
Li 6YE.'
Rl r,,R3
0 Ri
R2
R2
(A) (lb-1)
R
16 R6
00 0 5 R-- + ,N.,
R-- +
2 L- R4
L! O L 2
R2
\ R3 -----P'"_....
0 R1 0- Ri
0L1 0 Liy0
0 Li
II R
14 -sli
0 R--- + n
6 ,Nõ ,x.,
Rr L2- 0
(B) (1b-3) (1b-2)
B) Further additive components
The fuel additized with the inventive quaternized additive is a gasoline fuel
or especially
a middle distillate fuel, in particular a diesel fuel.
The fuel may comprise further customary additives to improve efficacy and/or
suppress
wear.
In the case of diesel fuels, these are primarily customary detergent
additives, carrier
oils, cold flow improvers, lubricity improvers, corrosion inhibitors,
demulsifiers,
dehazers, antifoams, cetane number improvers, combustion improvers,
antioxidants or
stabilizers, antistats, metallocenes, metal deactivators, dyes and/or
solvents.
In the case of gasoline fuels, these are in particular lubricity improvers
(friction
modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams,
combustion
CA 02804322 2013-01-03
32
improvers, antioxidants or stabilizers, antistats, metallocenes, metal
deactivators, dyes
and/or solvents.
Typical examples of suitable coadditives are listed in the following section:
B1) Detergent additives
The customary detergent additives are preferably amphiphilic substances which
possess at least one hydrophobic hydrocarbon radical with a number-average
molecular weight (Me) of 85 to 20 000 and at least one polar moiety selected
from:
(Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one
nitrogen
atom having basic properties;
(Db) nitro groups, optionally in combination with hydroxyl groups;
(Dc) hydroxyl groups in combination with mono- or polyamino groups, at least
one
nitrogen atom having basic properties;
(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
(De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(Df) polyoxy-C2- to C4-alkylene moieties terminated by hydroxyl groups, mono-
or
polyamino groups, at least one nitrogen atom having basic properties, or by
carbamate groups;
(Dg) carboxylic ester groups;
(Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino
and/or amido and/or imido groups; and/or
(Di) moieties obtained by Mannich reaction of substituted phenols with
aldehydes and
mono- or polyamines.
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33
The hydrophobic hydrocarbon 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. As typical
hydrophobic
hydrocarbon radicals, especially in conjunction with the polar moieties,
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 come into consideration.
Examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Da) are preferably
polyalkenemono-
or polyalkenepolyamines based on polypropene or on high-reactivity (i.e.
having
predominantly terminal double bonds) or conventional (i.e. having
predominantly
internal double bonds) polybutene or polyisobutene having Mn = 300 to 5000,
more
preferably 500 to 2500 and especially 700 to 2500. Such additives based on
high-
reactivity polyisobutene, which can be prepared from the polyisobutene which
may
comprise up to 20% by weight of n-butene units by hydroformylation and
reductive
amination with ammonia, monoamines or polyamines such as
dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine
or tetraethylenepentamine, are known especially from EP-A 244 616. When
polybutene
or polyisobutene having predominantly internal double bonds (usually in the 13
and 7
positions) are used as starting materials in the preparation of the additives,
a possible
preparative route is by chlorination and subsequent amination or by oxidation
of the
double bond with air or ozone to give the carbonyl or carboxyl compound and
subsequent amination under reductive (hydrogenating) conditions. The amines
used
here for the amination may be, for example, ammonia, monoamines or the
abovementioned polyamines. Corresponding additives based on polypropene are
described in particular in WO-A 94/24231.
Further particular additives comprising monoamino groups (Da) are the
hydrogenation
products of the reaction products of polyisobutenes having an average degree
of
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34
polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and
oxygen, as described in particular in WO-A 97/03946.
Further particular additives comprising monoamino groups (Da) are the
compounds
obtainable from polyisobutene epoxides by reaction with amines and subsequent
dehydration and reduction of the amino alcohols, as described in particular in
DE-A
196 20262.
Additives comprising nitro groups (Db), optionally in combination with
hydroxyl groups,
are preferably reaction products of polyisobutenes having an average degree of
polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of
nitrogen
oxides and oxygen, as described in particular in WO-A 96/03367 and in WO-A
96/03479. These reaction products are generally mixtures of pure
nitropolyisobutenes
(e.g. a,I3-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. a-
nitro43-
hydroxypolyisobutene).
Additives comprising hydroxyl groups in combination with mono- or polyamino
groups
(Dc) are in particular reaction products of polyisobutene epoxides obtainable
from
polyisobutene having preferably predominantly terminal double bonds and Mn =
300 to
5000, with ammonia or mono- or polyamines, as described in particular in EP-A
476 485.
Additives comprising carboxyl groups or their alkali metal or alkaline earth
metal salts
(Dd) are preferably copolymers of C2- to C40-olefins with maleic anhydride
which have a
total molar mass of 500 to 20 000 and some or all of whose carboxyl groups
have been
converted to the alkali metal or alkaline earth metal salts and any remainder
of the
carboxyl groups has been reacted with alcohols or amines. Such additives are
disclosed in particular by EP-A 307 815. Such additives serve mainly to
prevent valve
seat wear and can, as described in WO-A 87/01126, advantageously be used in
combination with customary fuel detergents such as poly(iso)buteneamines or
polyetheramines.
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
CA 02804322 2013-01-03
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
5 polyetheramines which are obtainable by reaction of C2- to Cscralkanols,
C6- to C30-
alkanediols, mono- or di-C2- to C30ralkylamines, Cl- to Caralkylcyclohexanols
or Cl- to
C30-alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide
and/or
butylene oxide per hydroxyl group or amino group and, in the case of the
polyetheramines, by subsequent reductive amination with ammonia, monoamines or
10 polyamines. Such products are described in particular in EP-A 310 875,
EP-A 356 725,
EP-A 700 985 and US-A 4 877 416. In the case of polyethers, such products also
have
carrier oil properties. Typical examples of these are tridecanol butoxylates,
isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol
butoxylates
and propoxylates and also the corresponding reaction products with ammonia.
Additives comprising carboxylic ester groups (Dg) are preferably esters of
mono-, di- or
tricarboxylic acids with long-chain alkanols or polyols, in particular those
having a
minimum viscosity of 2 mm2/s at 100 C, as described in particular in DE-A 38
38 918.
The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids,
and
particularly suitable ester alcohols or ester polyols are long-chain
representatives
having, for example, 6 to 24 carbon atoms. Typical representatives of the
esters are
adipates, phthalates, isophthalates, terephthalates and trimellitates of
isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products also have
carrier oil
properties.
Additives comprising moieties derived from succinic anhydride and having
hydroxyl
and/or amino and/or amido and/or especially imido groups (Dh) are preferably
corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride
and
especially the corresponding derivatives of polyisobutenylsuccinic anhydride
which are
obtainable by reacting conventional or high-reactivity polyisobutene having
Mr, =
preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500
to
2500, even more especially preferably 700 to 2500 and especially 800 to 1500,
with
maleic anhydride by a thermal route in an ene reaction or via the chlorinated
polyisobutene. The moieties having hydroxyl and/or amino and/or amido and/or
imido
groups are, for example, carboxylic acid groups, acid amides of monoamines,
acid
CA 02804322 2013-01-03
36
amides of di- or polyamines which, in addition to the amide function, also
have free
amine groups, succinic acid derivatives having an acid and an amide function,
carboximides with monoamines, carboximides with di- or polyamines which, in
addition
to the imide function, also have free amine groups, or diimides which are
formed by the
reaction of di- or polyamines with two succinic acid derivatives. In the
presence of
imido moieties D(h), the further detergent additive in the context of the
present
invention is, however, used only up to a maximum of 100% of the weight of
compounds
with betaine structure. Such fuel additives are common knowledge and are
described,
for example, in documents (1) and (2). They are preferably the reaction
products of
alkyl- or alkenyl-substituted succinic acids or derivatives thereof with
amines and more
preferably the reaction products of polyisobutenyl-substituted succinic acids
or
derivatives thereof with amines. Of particular interest in this context are
reaction
products with aliphatic polyamines (polyalkyleneimines) such as especially
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine,
pentaethylenehexamine and hexaethyleneheptamine, which have an imide
structure.
Additives comprising moieties (Di) obtained by Mannich reaction of substituted
phenols
with aldehydes and mono- or polyamines are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or polyamines
such
as ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine
or dimethylanninopropylamine. The polyisobutenyl-substituted phenols may stem
from
conventional or high-reactivity polyisobutene having Mr, = 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
CA 02804322 2013-01-03
37
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.
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 Gralkylene moieties which are obtainable by reacting
C2- to
Caralkanols, C6- to Cacralkanediols, mono- or di-C2- to C30-alkylamines, C1-
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 C -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.
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38
Further suitable carrier oil systems are described, for example, in DE-A 38 26
608,
DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
Examples of particularly suitable synthetic carrier oils are alcohol-started
polyethers
having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and
especially
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
10 straight-chain or branched C6- to Cm-alkyl radical. Particular examples
include
tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers
are the
reaction products (polyetherification products) of monohydric aliphatic Ce- to
C18-
alcohols with C3- to C6-alkylene oxides. Examples of monohydric aliphatic C6-
C18-
alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol,
decanol, 3-
15 propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol,
pentadecanol,
hexadecanol, octadecanol and the constitutional and positional isomers
thereof. The
alcohols can be used either in the form of the pure isomers or in the form of
technical
grade mixtures. A particularly preferred alcohol is tridecanol. Examples of C3-
to C6-
alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene
oxide, such
as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or
tetrahydrofuran,
pentylene oxide and hexylene oxide. Particular preference among these is given
to C3-
to C4-alkylene oxides, i.e. propylene oxide such as 1,2-propylene oxide and
butylene
oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
Especially
butylene oxide is used.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, as
described in
DE-A 10 102 913.
Particular carrier oils are synthetic carrier oils, particular preference
being given to the
above-described alcohol-started polyethers.
The carrier oil or the mixture of different carrier oils is added to the fuel
in an amount of
preferably 1 to 1000 ppm by weight, more preferably of 10 to 500 ppm by weight
and
especially of 20 to 100 ppm by weight.
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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 Cao-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 Cap-olefin monomers for the copolymers of class (K1) are, for
example,
those having 2 to 20 and especially 2 to 10 carbon atoms, and Ito 3 and
preferably 1
or 2 carbon-carbon double bonds, especially having one carbon-carbon double
bond.
In the latter case, the carbon-carbon double bond may be arranged either
terminally (a-
olefins) or internally. However, preference is given to a-olefins, more
preferably a-
olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene,
1-
hexene and in particular ethylene.
CA 02804322 2013-01-03
In the copolymers of class (K1), the at least one further ethylenically
unsaturated
monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters
and
further olefins.
5 When further olefins are also copolymerized, they are preferably higher
in molecular
weight than the abovementioned C2- to Co-olefin base monomer. When, for
example,
the olefin base monomer used is ethylene or propene, suitable further olefins
are in
particular C10- to Co-a-olefins. Further olefins are in most cases only
additionally
copolymerized when monomers with carboxylic ester functions are also used.
Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid
with C1- to
C20-alkanols, especially C1- to Cicralkanols, in particular with methanol,
ethanol,
propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol,
pentanol,
hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and
structural
isomers thereof.
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
hydrocarbon radical may be linear or branched. Among these, preference is
given to
the vinyl esters. Among the carboxylic acids with a branched hydrocarbon
radical,
preference is given to those whose branch is in the a-position to the carboxyl
group,
the a-carbon atom more preferably being tertiary, i.e. the carboxylic acid
being a so-
called neocarboxylic acid. However, the hydrocarbon radical of the carboxylic
acid is
preferably linear.
Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate,
vinyl
butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl
neononanoate, vinyl neodecanoate and the corresponding propenyl esters,
preference
being given to the vinyl esters. A particularly preferred alkenyl carboxylate
is vinyl
acetate; typical copolymers of group (K1) resulting therefrom are ethylene-
vinyl acetate
copolymers ("EVAs"), which are some of the most frequently used. Ethylene-
vinyl
acetate copolymers usable particularly advantageously and their preparation
are
described in WO 99/29748.
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41
Suitable copolymers of class (K1) are also those which comprise two or more
different
alkenyl carboxylates in copolymerized form, which differ in the alkenyl
function and/or
in the carboxylic acid group. Likewise suitable are copolymers which, as well
as the
alkenyl carboxylate(s), comprise at least one olefin and/or at least one
(meth)acrylic
ester in copolymerized form.
Terpolymers of a C2- to C40-a-olefin, a C.,- 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
Mõ
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 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.
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42
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 08- to Co-hydrocarbon radical. The nitrogen substituents may
also be
quaternized, i.e. be in cationic form. An example of such nitrogen compounds
is that of
ammonium salts and/or amides which are obtainable by the reaction of at least
one
amine substituted by at least one hydrocarbon radical with a carboxylic acid
having 1 to
4 carboxyl groups or with a suitable derivative thereof. The amines preferably
comprise
at least one linear C8- to Cao-alkyl radical. Primary amines suitable for
preparing the
polar nitrogen compounds mentioned are, for example, octylamine, nonylamine,
decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear
homologs. Secondary amines suitable for this purpose are, for example,
dioctadecylamine and methylbehenylamine. Also suitable for this purpose are
amine
mixtures, in particular amine mixtures obtainable on the industrial scale,
such as fatty
amines or hydrogenated tallamines, as described, for example, in Ullmann's
Encyclopedia of Industrial Chemistry, 6th Edition, "Amines, aliphatic"
chapter. Acids
suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid,
naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic
acid, and
succinic acids substituted by long-chain hydrocarbon radicals.
In particular, the component of class (K4) is an oil-soluble reaction product
of poly(C2-
to C2o-carboxylic acids) having at least one tertiary amino group with primary
or
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43
secondary amines. The poly(C2- to C20-carboxylic acids) which have at least
one
tertiary amino group and form the basis of this reaction product comprise
preferably at
least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl
groups. The
carboxylic acid units in the polycarboxylic acids have preferably 2 to 10
carbon atoms,
and are especially acetic acid units. The carboxylic acid units are suitably
bonded to
the polycarboxylic acids, usually via one or more carbon and/or nitrogen
atoms. They
are preferably attached to tertiary nitrogen atoms which, in the case of a
plurality of
nitrogen atoms, are bonded via hydrocarbon chains.
The component of class (K4) is preferably an oil-soluble reaction product
based on
poly(C2- to C20-carboxylic acids) which have at least one tertiary amino group
and are
of the general formula Ila orllb
HOOC,B B,COOH
I I
HOOC,õCOOH
B A. B
(11a)
-.
HOOCB N COOH
B., COON (11b)
in which the variable A is a straight-chain or branched C2- to C6-alkylene
group or the
moiety of the formula III
HOOCB CH2-CH2-
CH2-CH2-
(11I)
and the variable B is a C1- to C19-alkylene group. The compounds of the
general
formulae Ila and I lb especially have the properties of a WASA.
Moreover, the preferred oil-soluble reaction product of component (K4),
especially that
of the general formula Ila or 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.
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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 C19-alkylene groups of the variable B are, for example, 1,2-ethylene,
1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene,
dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene,
nonadecamethylene and especially methylene. The variable B comprises
preferably 1
to 10 and especially 1 to 4 carbon atoms.
The primary and secondary amines as a reaction partner for the polycarboxylic
acids to
form component (K4) are typically monoamines, especially aliphatic monoamines.
These primary and secondary amines may be selected from a multitude of amines
which bear hydrocarbon radicals which may optionally be bonded to one another.
These parent amines of the oil-soluble reaction products of component (K4) are
usually
secondary amines and have the general formula HN(R8)2 in which the two
variables R8
are each independently straight-chain or branched Cio- to C30-alkyl radicals,
especially
C14- to C24-alkyl radicals. These relatively long-chain alkyl radicals are
preferably
straight-chain or only slightly branched. In general, the secondary amines
mentioned,
with regard to their relatively long-chain alkyl radicals, derive from
naturally occurring
fatty acid and from derivatives thereof. The two R8 radicals are preferably
identical.
The secondary amines mentioned may be bonded to the polycarboxylic acids by
means of amide structures or in the form of the ammonium salts; it is also
possible for
only a portion to be present as amide structures and another portion as
ammonium
salts. Preferably only few, if any, free acid groups are present. The oil-
soluble reaction
products of component (K4) are preferably present completely in the form of
the amide
structures.
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
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group, of dioleylamine, dipalmitinamine, dicoconut fatty amine,
distearylamine,
dibehenylamine or especially ditallow fatty amine. A particularly preferred
component
(K4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4
mol of
hydrogenated ditallow fatty amine.
5
Further typical examples of component (K4) include the N,N-dialkylammonium
salts of
2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mol of
phthalic
anhydride and 2 mol of ditallow fatty amine, the latter being hydrogenated or
unhydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone
with
10 2 mol of a dialkylamine, for example ditallow fatty amine and/or tallow
fatty amine, the
last two being hydrogenated or unhydrogenated.
Further typical structure types for the component of class (K4) are cyclic
compounds
with tertiary amino groups or condensates of long-chain primary or secondary
amines
15 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
20 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
25 least two different (meth)acrylic esters which differ with regard to the
esterified alcohol.
The copolymer optionally comprises another different oleflnically 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
30 groups having been neutralized with hydrogenated tallannine. 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
35 weight, more preferably of 20 to 2000 ppm by weight, even more
preferably of 50 to
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1000 ppm by weight and especially of 100 to 700 ppm by weight, for example of
200 to
500 ppm by weight.
B4) Lubricity improvers
Suitable lubricity improvers or friction modifiers are based typically on
fatty acids or
fatty acid esters. Typical examples are tall oil fatty acid, as described, for
example, in
WO 98/004656, and glyceryl monooleate. The reaction products, described in US
6 743 266 B2, of natural or synthetic oils, for example triglycerides, and
alkanolamines
are also suitable as such lubricity improvers.
B5) Corrosion inhibitors
Suitable corrosion inhibitors are, for example, succinic esters, in particular
with polyols,
fatty acid derivatives, for example oleic esters, oligomerized fatty acids,
substituted
ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie
Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
B6) Demulsifiers
Suitable demulsifiers are, for example, the alkali metal or alkaline earth
metal salts of
alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or
alkaline
earth metal salts of fatty acids, and also neutral compounds such as alcohol
alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-
butylphenol
ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols,
condensation
products of ethylene oxide (EO) and propylene oxide (PO), for example
including in the
form of EO/P0 block copolymers, polyethyleneimines or else polysiloxanes.
B7) Dehazers
Suitable dehazers are, for example, alkoxylated phenol-formaldehyde
condensates, for
example the products available under the trade names NALCO 7D07 (Nalco) and
TOLAD 2683 (Petrolite).
B8) Antifoams
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Suitable antifoams are, for example, polyether-modified polysiloxanes, for
example the
products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907
(Dow Corning) and RHODOSIL (Rhone Poulenc).
B9) Cetane number improvers
Suitable cetane number improvers are, for example, aliphatic nitrates such as
2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-
butyl peroxide.
B10) Antioxidants
Suitable antioxidants are, for example substituted phenols, such as 2,6-di-
tert-
butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines
such as
N,N'-di-sec-butyl-p-phenylenediamine.
B11) Metal deactivators
Suitable metal deactivators are, for example, salicylic acid derivatives such
as
N,N'-disalicylidene-1,2-propanediamine.
B12) Solvents
Suitable solvents are, for example, nonpolar organic solvents such as aromatic
and
aliphatic hydrocarbons, for example toluene, xylenes, white spirit and
products sold
under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL
(DownMobil), and also polar organic solvents, for example, alcohols such as
2-ethylhexanol, decanol and isotridecanol. Such solvents are usually added to
the
diesel fuel together with the aforementioned additives and coadditives, which
they are
intended to dissolve or dilute for better handling.
C) Fuels
The inventive additive is outstandingly suitable as a fuel additive and can be
used in
principle in any fuels. It brings about a whole series of advantageous effects
in the
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operation of internal combustion engines with fuels. Preference is given to
using the
inventive quaternized additive in middle distillate fuels, especially diesel
fuels.
The present invention therefore also provides fuels, especially middle
distillate fuels,
with a content of the inventive quaternized additive which is effective as an
additive for
achieving advantageous effects in the operation of internal combustion
engines, for
example of diesel engines, especially of direct-injection diesel engines, in
particular of
diesel engines with common-rail injection systems. This effective content
(dosage) is
generally 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight,
especially
25 to 1000 ppm by weight, in particular 30 to 750 ppm by weight, based in each
case
on the total amount of fuel.
Middle distillate fuels such as diesel fuels or heating oils are preferably
mineral oil
raffinates which typically have a boiling range from 100 to 400 C. These are
usually
distillates having a 95% point up to 360 C or even higher. These may also be
so-called
"ultra low sulfur diesel" or "city diesel", characterized by a 95% point of,
for example,
not more than 345 C and a sulfur content of not more than 0.005% by weight or
by a
95% point of, for example, 285 C and a sulfur content of not more than 0.001%
by
weight. In addition to the mineral middle distillate fuels or diesel fuels
obtainable by
refining, those obtainable by coal gasification or gas liquefaction ["gas to
liquid" (GTL)
fuels] or by biomass liquefaction ["biomass to liquid" (BTL) fuels] are also
suitable. Also
suitable are mixtures of the aforementioned middle distillate fuels or diesel
fuels with
renewable fuels, such as biodiesel or bioethanol.
The qualities of the heating oils and diesel fuels are laid down in detail,
for example, in
DIN 51603 and EN 590 (cf. also Ullmann's Encyclopedia of Industrial Chemistry,
5th
edition, Volume Al2, p. 617 ff.).
In addition to the use thereof in the abovementioned middle distillate fuels
of fossil,
vegetable or animal origin, which are essentially hydrocarbon mixtures, the
inventive
quaternized additive can also be used in mixtures of such middle distillates
with biofuel
oils (biodiesel). Such mixtures are also encompassed by the term "middle
distillate fuel"
in the context of the present invention. They are commercially available and
usually
comprise the biofuel oils in minor amounts, typically in amounts of 1 to 30%
by weight,
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=
49
especially of 3 to 10% by weight, based on the total amount of middle
distillate of fossil,
vegetable or animal origin and biofuel oil.
Biofuel oils are generally based on fatty acid esters, preferably essentially
on alkyl
esters of fatty acids which derive from vegetable and/or animal oils and/or
fats. Alkyl
esters are typically understood to mean lower alkyl esters, especially Cl-C4-
alkyl
esters, which are obtainable by transesterifying the glycerides which occur in
vegetable
and/or animal oils and/or fats, especially triglycerides, by means of lower
alcohols, for
example ethanol or in particular methanol ("FAME"). Typical lower alkyl esters
based
on vegetable and/or animal oils and/or fats, which find use as a biofuel oil
or
components thereof, are, for example, sunflower methyl ester, palm oil methyl
ester
("PME"), soya oil methyl ester ("SME") and especially rapeseed oil methyl
ester
("RME").
The middle distillate fuels or diesel fuels are more preferably those having a
low sulfur
content, i.e. having a sulfur content of less than 0.05% by weight, preferably
of less
than 0.02% by weight, more particularly of less than 0.005% by weight and
especially
of less than 0.001% by weight of sulfur.
Useful gasoline fuels include all commercial gasoline fuel compositions. One
typical
representative which shall be mentioned here is the Eurosuper base fuel to EN
228,
which is customary on the market. In addition, gasoline fuel compositions of
the
specification according to WO 00/47698 are also possible fields of use for the
present
invention.
The inventive quaternized additive is especially suitable as a fuel additive
in fuel
compositions, especially in diesel fuels, for overcoming the problems outlined
at the
outset in direct-injection diesel engines, in particular in those with common-
rail injection
systems.
The invention is now illustrated in detail by the working examples which
follow:
Experimental section:
=
A. General test methods
a) Determination of the amide or imide content by IR spectroscopy
5 The presence of amide or imide in a sample is examined by IR spectroscopy.
The
characteristic IR band for amide is at 1667 5 cm-1, whereas the
characteristic IR band
of the imide is at 1705 5 cm-1.
For this purpose, the samples were diluted 50% (m/m) in Solvesso TM and
analyzed in a
10 29 pm CaF2 Guyette.
b) Engine test
b1) XUD9 test ¨ determination of flow restriction
The procedure was according to the standard stipulations of CEC F-23-1-01.
b2) DW10 test ¨ determination of power loss as a result of injector deposits
in the
common-rail diesel engine
To examine the influence of the additives on the performance of direct-
injection diesel
engines, the power loss was determined on the basis of the official test
method
CEC F-098-08. The power loss is a direct measure of formation of deposits in
the
injectors.
A direct-injection diesel engine with common-rail system according to test
method
CEC F-098-08 was used. The fuel used was a commercial diesel fuel from
Haltermann
(RF-06-03). To synthetically induce the formation of deposits at the
injectors, 1 ppm of
zinc was added thereto in the form of a zinc didodecanoate solution. The
results
illustrate the relative power loss at 4000 rpm, measured during 12 hours of
constant
operation. The value "t0" indicates the power loss normalized (100%) to the
value after
10 minutes; the value "t1" indicates the power loss normalized to the value
after one
hour.
c) Brief sedimentation test (BS test) - determination of action as a cold flow
improver
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In the course of storage of diesel fuels in a storage or vehicle tank at
temperatures
below the cloud point (CP), precipitated paraffins can settle out. The
paraffin-rich
bottom phase which forms has a relatively poor cold performance, and can block
filters
of vehicles, thus leading to collapse of the delivery rate.
The BS test simulates and visually evaluates possible sedimentation in vehicle
tanks.
The CP and CFPP values of the diesel fuel phase enriched with paraffins
obtained in
the test are determined. The comparison of these values with those for the
unsedimented fuel permits conclusions about the cold performance of the fuel.
For this
purpose, delta CP or delta CFPP values are determined.
In the test, the optionally additized diesel fuel (DF) to be tested is
processed at ¨13 C
for a total of 16 h. It is assessed visually. Subsequently, 80% by volume of
upper phase
of the fuel is sucked out cautiously from the top. After heating and
homogenizing the
remaining 20% lower phase, the cloud point (CPCC) and the cold filter plugging
point
(CFPPCC) thereof are determined with apparatus known per se.
The procedure is to filter the amounts of sample required through a fluted
filter (to
DIN EN 116) to remove soil, coke constituents, water or other undissolved
impurities.
The sample vessel (scaled measuring cylinder) is filled with 550 ml of sample
liquid. If
required, the sample is admixed with additive. It is heated to 50 C in a water
bath. The
sample vessel is removed from the water bath and dried. The sample is
homogenized
by inverting and shaking. The starting CP and CFPP values ("original") of
portions are
determined. The sample temperature is adjusted to close to 25 C by standing
under
air.
The sample vessel containing 500 ml of sample is suspended in a liquid bath by
means
of a holding device. Heat treatment begins at 25 C. The sample is cooled to -
13 C
within 2 h 40 min. The sample is stored at -13 C for 13 h 20 min.
By means of a suction device, the sample is sucked out from the top down to a
residual
amount of 100 ml (20%). Sample movement and turbulence should be kept as low
as
possible. The sample vessel with the 20% lower phase remaining therein is
heated to
50 C. The lower phase is homogenized and used to determine the final values of
CP
and CFPP (i.e. CPCC and CFPPCC).
52
d) Detection of the betaine structure
The betaine structure in inventive additives and the synthesis precursors
thereof is
detected by determination of mass using Matrix Assisted Laser
Desorption/Ionization-
Time Of Flight Mass Spectrometry (MALDI-TOF-MS). The analysis is effected
under
the following conditions:
The BIFLEX 3 instrument from Bruker and a UV laser of wavelength 337 nm are
used.
The laser power is increased until the ionization threshold of the ions is
attained. The
matrix consists of 20 g/I of dithranol in THF (ion-exchanged), using a polymer
concentration of approx. 2 g/I in THF. The procedure is as follows: the matrix
is mixed
with the particular polymer in a ratio of 1:1, and 1 pl thereof is dried on
the target
("dried-droplet technique"). The dried fractions are then dissolved in 20 pl
of the matrix
solution and finally analyzed. A total of 100 individual spectra are added up
per
measurement.
In addition, analysis is also effected by means of ESI-LC/MS (electrospray
ionization
liquid chromatography-mass spectrometry) in the solvent THE. For this purpose,
the
LTQ/FT (Thermo) MS system and the LC system consisting of HP 1100 bin pump,
HP 1100 ALS and HP 1100 DAD are used. Approx. 10 mg of test substance are
dissolved in 1 ml of THF and analyzed at room temperature. The resolution is
100 000.
e) Determination of the motor oil compatibility of diesel fuels (DF)
The determination was effected by the methods in the catalog of criteria
compiled by
the DGMK German Society for Petroleum and Coal for the testing of lubricity
additives
in diesel fuels (DGMK Report 531).
In the fuel system of diesel vehicles, it is possible that small amounts of
motor oil get
into the diesel fuel circuit. In some cases, it has been observed that
reactions occurred
between motor oil constituents and the additives present in diesel fuels, and
led to
blockages of fuel filters and hence to the failure of vehicles. Therefore, a
test method
was developed, with the aid of which reactions between motor oil and diesel
fuel
additives which would lead to filter blockages are recognized and assessed.
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The additive to be tested is mixed with the same amount of the stipulated
motor oil and
conditioned at 90 C over three days. After this conditioning, the mixture is
diluted with
diesel fuel and mixed, and assessed with the aid of the SEDAB test (DGMK
Report
531, appendix II-A). The results from both tests permit a statement about the
"motor oil
compatibility" of the diesel fuel additive to be tested.
Equipment and test media:
- 500 ml Erlenmeyer flask with NS19 ground glass stopper
- alpha-methylnaphthalene
- diesel fuel which passes the SEDAB test impeccably
- motor oil (CEC Reference Lube RL-189, SAE 15W-40)
The OF provided for performance of the test and the motor oil should be
assessed with
the aid of the SEDAB test before the first use thereof. For this purpose, 10 g
of motor
oil are dissolved in 500 ml of OF. To improve the solubility, it may be
necessary to add
10 ml of alpha-methylnaphthalene and repeat the homogenization. This mixture
is
assessed immediately in the SEDAB test. When the mixture is filterable
impeccably,
the DF can be used for the performance of the testing.
10 g of motor oil and 10 g of the additive to be tested are each weighed into
a 500 ml
Erlenmeyer flask, and then homogenized by tilting the flask. In the case of
poor
miscibility, 10 ml of alpha-methylnaphthalene are additionally added and the
mixture is
homogenized again. This mixture is closed with a glass stopper and conditioned
at a
temperature of 90 C in a drying cabinet for three days.
After conditioning, the mixture is allowed to cool at room temperature for one
hour and
assessed visually for any deposits, turbidity, gel formation, etc. The mixture
is made up
to 500 ml with diesel fuel and mixed thoroughly. It is assessed visually.
Should deposits
have formed, they should be suspended by vigorous shaking before the
performance
of the SEDAB test. After standing for two hours, the mixture is assessed
visually again
and then filtered through a 0.8 pm filter at a pressure differential of 800
mbar (see
SEDAB test method). The total amount has to be filterable within the fixed
time.
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54
In the case of occurrence of deposits, turbidity, gel formation and/or poor
filterability in
the SEDAB test, the additive cannot be classified as motor oil-compatible. In
the case
of good filterability and impeccable visual appearance, the additive can be
classified as
motor oil-compatible.
Specifications for the SEDAB test:
500 ml of a pretreated DF are sucked through a membrane filter. The time in
seconds
needed for this volume to filter at 20 2 C and 200 hPa (i.e. pressure
differential
approx. 800 hPa) is determined. When this is more than two minutes, the amount
of
filtrate present after two minutes is noted.
Instruments/materials required
= Membrane filter: from Sartorius, made of cellulose nitrate, white,
smooth, diameter
50 mm, pore size 0.8 pm.
= Filtration apparatus: filtration unit with 500 ml funnel: Sartorius SM 16
201
= Suction bottle: capacity 1000 ml
= Vacuum system: e.g. constant-vacuum TOM-VAC 1 Automatic Zerosystem
with a minimum pressure of 200 hPa.
= Drying cabinet for heat treatment at 90 3 C, without air circulation
= Tweezers
= Glass Petri dish, diameter approx. 125 mm, with acceptable lid
= Sample vessel: measuring cylinder (capacity 500 ml) with glass joint and
stopper.
To prepare the sample, the sample vessel of the original fuel sample is shaken
with 20
vertical strokes. The sample is left to stand at room temperature for 16
hours.
Immediately before the measurement, the fuel is homogenized once again by
shaking
(10 strokes) and introduced into the 500 ml funnel of the test apparatus.
The membrane filters are conditioned at 90 3 C for a half hour in a drying
cabinet
and then stored in a desiccator until use. The correspondingly prepared
membrane
filter is placed into the filtration apparatus. The 500 ml funnel is filled
with the entire
sample (500 ml) and then a pressure of 200 hPa (absolute, corresponds to
pressure
differential approx. 800 hPa) is immediately applied. It should be ensured
that no fuel
sample is poured in thereafter. The filtration time is reported rounded to
full seconds. If
CA 02804322 2013-01-03
a filtration time of two minutes is exceeded without the entire sample being
filtered, the
test is ended and the volume of the fuel which has passed through to that
point is
measured. In this case, the result is reported as "> 2 minutes" and the amount
of
sample (m1) filtered by the time the test was stopped. When the filtration
time of the
5 sample is more than two minutes, a corresponding specimen should be
heated to 50 C
for 30 minutes and then filtered. If the test result is again above two
minutes, the total
soil content of the fuel should be determined to DIN 51 419.
After the filtration, funnel and filter are rinsed with n-heptane and then
with petroleum
spirit (40/80) to free them of DF. The membrane filter is cautiously removed
from the
10 filter plate with tweezers, placed into a clean Petri dish and dried in
a drying cabinet at
90 3 C with the lid half-open for 30 minutes. Thereafter, the Petri dish is
placed into
the desiccator for cooling for at least 15 minutes.
Samples which are filterable within two minutes by the above-described process
are
15 classified as "uncritical" with regard to the present test method.
Diesel fuels which are
not filterable within this time should be classified as "critical" and can
lead to filter
blockages in vehicles and at filling stations. In the case of samples with
critical
behavior, the membrane filter should be studied optically (microscopically) or
by means
of infrared spectroscopy for the cause of the blockage.
B. Preparation and analysis examples:
Reactants used:
P1BSA: Mw = 1100; hydrolysis number = 85 mg KOH/g
DMAPA: Mw = 102.18
Styrene oxide: Mw = 120.15
Acetic acid: Mw = 60.05
Preparation example 1: synthesis of an inventive acid-free quatemized
succinamide
(PIBSA/DMAPA/styrene oxide; amidation at 400C)
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0
0 +
Solvesso 150 OH
e
0 0
0 0 H=
=
70 C /7 hi N2
0 0
(A)
386.8 g (0.35 mol) of polyisobutenesuccinic anhydride (PIBSA 1000) are
dissolved in
176 g of Solvesso 150 in a 2-liter four-necked flask at room temperature under
a gentle
.. N2 stream. After the addition of 29.9 g (0.29 mol) of 3-dimethylamino-1-
propylamine
(DMAPA), the reaction temperature rises to 40 C. The solution is stirred at 40
C for 10
minutes. Subsequently, 34.2 g (0.29 mol) of (1,2-epoxyethyl)benzene are added,
which
is followed by a further reaction time of 7 hours at 70 C under N2. The
solution is finally
adjusted to an active ingredient content of 50% with 274.9 g of Solvesso 150.
By IR analysis, it was possible to detect the formation of the inventive amide
addition
product (A).
By means of ESI-LC/MS and MALDI-TOF-MS, the betaine structure of (A) was
determined experimentally.
Preparation example 2 (comparison): synthesis of an acid-containing quatemized
succinimide (PIBSA/DMAPA/styrene oxide/acetic acid) analogously to
W020061135881
57
O 0 N¨
HNN
H
150 C/ 3h/N,
0 +
Pilot 900
11 11
O 0
Ac _
,
O N¨ = 0 /
approx. 70'C / 5 h / N2 ¨N
N OH
+ 110acetic acid
O 0
(B)
The overall experiment is performed under a gentle N2 stream. The initial
charge of
PIBSA 1000 (481.61 g) and PilotTm 900 oil (84.99 g) is stirred at 110 C. Then
DMAPA
(37.28g) is metered in at 110-115 C within 42 minutes. A slightly exothermic
reaction
is observed. Subsequently, the mixture is heated to 150 C and stirred at 150 C
for 3 h
to remove water of reaction. The mixture is then cooled to room temperature,
and
successively admixed with Me0H (152 g), acetic acid (21.91 g) and styrene
oxide
(43.84 g). The mixture is then stirred at reflux (67-69 C) for 5 h. After
standing at 30-
35 C overnight, the mixture is concentrated by distillation (1 h/6 mbar/36 C
oil bath).
The final weight of 661.1 g is adjusted to an active ingredient content of 50%
with
PilotT" 900 oil (493.07 g).
By IR analysis, it was possible to detect the formation of the imide (B).
By means of ESI-LC/MS and MALDI-TOF-MS, the absence of a betaine structure in
(B)
was demonstrated experimentally.
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. The following packages were used:
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M2450: Inventive additive package
Additive Proportion (%)
Product according 48.06
to Prep. Ex. 1
Dehazer 0.92
Antifoam 1.11
Solvesso 150 25.88
Pilot 900 24.03
Sum 100
M2452: Comparative additive package
Additive Proportion (%)
Product according 48.06
to Prep. Ex. 2
Dehazer 0.92
Antifoam 1.11
Solvesso 150 49.91
Sum 100
Use example 1: determination of the additive action on the formation of
deposits in
diesel engine injection nozzles
a) XUD9 Tests
Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
The results are compiled in the table which follows:
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Ex. Designation Active Active ingredient Flow
restriction
ingredient dosage in the fuel 0.1 mm needle
dosage [mg/kg] stroke
[mg/kg] [%l
#1 Blank value 61
#2 Additive according to 60 30 4.2
preparation example 1
b) DW10 Test
The test results are shown in figure 1. The tO values are plotted therein.
It is found that, at the same dosage (100 mg/kg of active ingredient, i.e. 200
ppm of
preparation example 1), the inventive amide additive (rhombuses) and the imide
comparative additive (triangles) significantly reduce the power loss observed
for
unadditized fuel (squares), although the inventive additive stabilizes the
remaining
power loss in the region of about 0.5% over the entire test duration, i.e.
99.5% of the
original maximum engine power is maintained. With the corresponding
comparative
additive, however, only a power of 98.5% of the original maximum engine power
is
maintained.
Use example 2: determination of the low-temperature properties ¨ brief
sedimentation
test
Commercially available winter OF was additized in the manner specified in the
table
below with additive according to preparation example 1 (#3) and additive
according to
preparation example 2 (#2), and also with additive package M2450 (#5) or M2452
(#4),
and subjected to a BS test. The comparison (#1) used was DF with cold flow
improver
additive without amide and imide.
The test fuel used was diesel fuel from Bayernoil, (CP ¨6.5 C).
All fuel samples (#1 to #5) were additionally additized with commercial middle
distillate
cold flow improver (MDFI) and wax antisettling additive (WASA).
=
CA 02804322 2013-01-03
It can be inferred from the test data compiled in the table which follows that
the delta
CP and CFPPCC values of the DFs additized in accordance with the invention are
significantly improved compared to the imide-containing DFs. The amide
additization
can thus significantly improve the cold performance of the DFs.
5
#1 #2 #3 #4 #5
130 ppm 130 ppm 270.5 ppm 270.5 ppm
M2452 M2450
Comparison Invention Comparison Invention
(Prep. Ex. 2) (Prep. Ex. 1) (Prep. Ex. 2) (Prep.
Ex. 1)
CP CFPP CP CFPP CP CFPP CP CPP CP CFPP
-6.5 -27 -27 -27 -27 -27
CPCC CFPPCC CPCC CFPPCC CPCC CFPPCC CPCC CFPPCC CPCC CFPPCC
-3.3 -20 -3.8 -21 -6.2 -28 -1.8 -20 -6.1 -28
Delta CP -- Delta CP ¨ Delta CP -- Delta CP -- Delta
CP ---
3.2 2.7 ¨ 0.3 4.7 ¨ 0.4
CFPP: CFPP of the overall fuel
CFPPCC: CFPP of the lower phase
CPCC: CP of the lower phase
Delta CP: Difference from the CP of the fuel additized only with cold flow
improver
10 without addition of preparation example 1 or 2
Use example 3: Determination of motor oil compatibility
The determination was effected according to the specifications of DGMK Report
531.
15 Motor oil used: Wintershall 14W40 Multi Record Top
Diesel fuel (DE) used: RF-06-03 (reference diesel, Haltermann Products,
Hamburg)
The additive to be tested is mixed with the same amount of mineral oil (10 g
each
time), conditioned at 90 C for 3 days and assessed visually in the course
thereof.
20 Subsequently, the mixture is made up to 500 ml with diesel fuel, mixed
and assessed
with the aid of the SEDAB filtration test (likewise defined in DGMK Report
531).
The results are compiled in the table which follows:
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Test # Producta) Visual Solubility Filtration
(from preparation 72 h/90 C in OF
ex. X)
1 2 solid turbid, fail
(comparison) (fail) insoluble
2 1 liquid soluble pass
(invention) (pass)
a) since both products comprised different types of solvent (Solvesso 150 or
Pilot 900)
as a result of the synthesis, they were admixed with the same amount of the
other
solvent in each case before performance of the test, so as to give identical
test
conditions.
Use example 4: Determination of the effect of IDIDs
The determination was effected in a passenger vehicle operating test.
Commercial
diesel fuel (DF) EN590 was additized (with customary OF additives). The
additive to be
tested (inventive additive according to preparation example 1) was added to
the EN590
OF. For comparison, commercial EN590 fuel which has not been admixed with an
inventive additive was used. After the engine test had ended, the injectors
were
checked for deposits. A surprisingly clear positive effect on I DIDs is
observed.
Test procedure:
A passenger vehicle with common-rail injectors (magnet type), in which
injector
deposits had been found, was used for evaluation of the additive for removal
of these
internal injector deposits.
The occurrence of brownish internal deposits in the injectors was detected by
visual
inspection of the solenoid coil face, of the valve plate in front of the face
and of the
valve seat face, and was also noticeable through rough and noisy engine
running. It
was likewise possible to infer from the readout data that the amount of the
fuel volume
injected into the cylinder deviated distinctly from the normal value.
The engine was first operated on the road with the tank filled with
conventionally
additized diesel without inventive additive, EN590 base fuel (50 liters, 750
km in mixed
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operation on freeways, other major roads and downtown). No improvement in the
internal deposits was observed when the vehicle was operated with a tank
filled with
unadditized fuel (cf. table below).
In the next step, the tank was filled with the same EN590 base fuel, but which
had
been admixed with the inventive additive in a dosage of 120 mg/kg of active
material.
The car was run again for 750 km in mixed operation. The deposits after 750 km
were
distinctly reduced after this test operation with additized fuel, as was
already detectable
by softer, quieter engine operation. The readout data from the engine control
unit also
showed that the amounts of fuel injected declined to the target value.
After two tank fillings and operation over 1500 km with fuel additized in
accordance
with the invention, the brownish injector deposits had disappeared completely
from the
solenoid coil face, the valve plate in front of the face and the valve seat
face, as was
discernible visually after the injector had been opened.
These results illustrate clearly that the inventive additive completely
removed internal
injector deposits (IDIDs) at low dosage. It can likewise be concluded from the
test
results that the additive is also capable of preventing the formation of IDIDs
even at low
dosage rates. Furthermore, it was found that the inventive additive is capable
of
eliminating not only wax- or soap-like IDIDs but also solid, carbon-like
polymeric
deposits.
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Table
Status Test Test km Engine Visual Data from Result
km with running inspection ECU
total additized (solenoid coil
fuel face)
Standard 0 0 rough, severe injected severe
vehicle for loud brownish fuel volume deposits
field deposits outside (carbon-
operation target value containing)
1st tank 750 0 rough, severe injected no
filling + loud brownish fuel volume improvement,
running with deposits outside severe
unadditized target value deposits
fuel (EN590 (carbon-
base fuel) containing)
1st tank 1500 750 quieter reduced injected reduced
filling + deposits fuel volume deposits
running with within
additized target value
fuel (dosage
120 mg/kg)
2nd tank 2250 1500 gentle, deposits injected deposits
filling + quiet completely fuel volume completely
running with disappeared within disappeared
additized target value
fuel (dosage
120 mg/kg)
Reference is made explicitly to the disclosure of the publications cited
herein.
