U.S. patent application number 13/712297 was filed with the patent office on 2013-11-07 for use of quaternized alkyl amines as additive in fuels and lubricants.
The applicant listed for this patent is Harald BOEHNKE, Wolfgang GRABARSE, Markus HANSCH, Jan STRITTMATTER, Ludwig VOELKEL. Invention is credited to Harald BOEHNKE, Wolfgang GRABARSE, Markus HANSCH, Jan STRITTMATTER, Ludwig VOELKEL.
Application Number | 20130296210 13/712297 |
Document ID | / |
Family ID | 49512985 |
Filed Date | 2013-11-07 |
United States Patent
Application |
20130296210 |
Kind Code |
A1 |
HANSCH; Markus ; et
al. |
November 7, 2013 |
USE OF QUATERNIZED ALKYL AMINES AS ADDITIVE IN FUELS AND
LUBRICANTS
Abstract
The present invention relates to the use of quaternized
alkylamine nitrogen compounds as a fuel additive and lubricant
additive, such as, more particularly, as a detergent additive; for
reduction or prevention of deposits in the injection systems of
direct injection diesel engines, especially in common rail
injection systems, for reduction of the fuel consumption of direct
injection diesel engines, especially of diesel engines with common
rail injection systems, and for minimization of power loss in
direct injection diesel engines, especially in diesel engines with
common rail injection systems; and as an additive for gasoline
fuels, especially for operation of DISI engines.
Inventors: |
HANSCH; Markus; (Speyer,
DE) ; BOEHNKE; Harald; (Mannheim, DE) ;
VOELKEL; Ludwig; (Limburgerhof, DE) ; GRABARSE;
Wolfgang; (Mannheim, DE) ; STRITTMATTER; Jan;
(Xuhui district, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HANSCH; Markus
BOEHNKE; Harald
VOELKEL; Ludwig
GRABARSE; Wolfgang
STRITTMATTER; Jan |
Speyer
Mannheim
Limburgerhof
Mannheim
Xuhui district |
|
DE
DE
DE
DE
CN |
|
|
Family ID: |
49512985 |
Appl. No.: |
13/712297 |
Filed: |
December 12, 2012 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61569335 |
Dec 12, 2011 |
|
|
|
Current U.S.
Class: |
508/547 ; 44/422;
564/292 |
Current CPC
Class: |
C10L 2200/0476 20130101;
C10L 1/1883 20130101; C10M 133/04 20130101; C10M 133/06 20130101;
C10L 2200/0446 20130101; C10M 2215/04 20130101; C10M 2207/123
20130101; C10N 2030/04 20130101; C10L 1/222 20130101; C10L 2270/026
20130101; C10L 1/1895 20130101; C10N 2040/253 20200501; C10L 1/189
20130101; C10L 1/2222 20130101; C10L 10/04 20130101; C10L 2200/0423
20130101; C10L 10/18 20130101; C10M 2207/126 20130101; C10M
2207/288 20130101; C10L 1/1881 20130101; C10L 1/1905 20130101; C10L
10/06 20130101; C10L 2270/023 20130101 |
Class at
Publication: |
508/547 ;
564/292; 44/422 |
International
Class: |
C10L 1/222 20060101
C10L001/222; C10M 133/04 20060101 C10M133/04 |
Claims
1. The use of a reaction product comprising a quaternized nitrogen
compound, or of a fraction thereof which comprises a quaternized
nitrogen compound and is obtained from the reaction product by
purification, said reaction product being obtainable by reacting a
quaternizable alkylamine comprising at least one quaternizable
tertiary amino group with a quaternizing agent which converts the
at least one tertiary amino group to a quaternary ammonium group,
the quaternizing agent being the alkyl ester of a cycloaromatic or
cycloaliphatic mono- or polycarboxylic acid, especially of a mono-
or dicarboxylic acid, or of an aliphatic polycarboxylic acid,
especially dicarboxylic acid, a hydrocarbyl epoxide, optionally in
combination with a free acid, or a dialkyl carbonate; as a fuel
additive or lubricant additive.
2. The use according to claim 1 as an additive for reducing the
fuel consumption of direct injection diesel engines, especially of
diesel engines with common rail injection systems, and/or for
minimizing power loss in direct injection diesel engines,
especially in diesel engines with common rail injection
systems.
3. The use according to claim 1 as a gasoline fuel additive for
reducing the level of deposits in the intake system of a gasoline
engine, such as especially DISI and PFI (port fuel injector)
engines.
4. The use according to claim 1 as a diesel fuel additive for
reducing and/or preventing deposits in the injection systems, such
as, more particularly, the internal diesel injector deposits
(IDIDs), and/or valve sticking in direct injection diesel engines,
especially in common rail injection systems.
5. The use according to any of the preceding claims, wherein the
alkylamine comprises at least one compound of the following general
formula 3 R.sub.aR.sub.bR.sub.cN (3) in which at least one of the
R.sub.a, R.sub.b and R.sub.c radicals is a straight-chain or
branched, saturated or unsaturated C.sub.8-C.sub.40-hydrocarbyl
radical (especially straight-chain or branched
C.sub.8-C.sub.40-alkyl) and the remaining radicals are identical or
different, straight-chain or branched, saturated or unsaturated
C.sub.1-C.sub.6-hydrocarbyl radicals (especially
C.sub.1-C.sub.6-alkyl); or in which all R.sub.a, R.sub.b and
R.sub.c radicals are identical or different, straight-chain or
branched, saturated or unsaturated C.sub.8-C.sub.40-hydrocarbyl
radicals, especially straight-chain or branched
C.sub.8-C.sub.40-alkyl radicals.
6. The use according to any of the preceding claims, wherein the
quaternizing agent is a compound of the general formula 1
R.sub.1OC(O)R.sub.2 (1) in which R.sub.1 is a lower alkyl radical
and R.sub.2 is an optionally substituted monocyclic aryl or
cycloalkyl radical, where the substituent is selected from OH,
NH.sub.2, NO.sub.2, C(O)OR.sub.3, and R.sub.1OC(O)--, in which
R.sub.1 is as defined above and R.sub.3 is H or R.sub.1.
7. The use according to any of claims 1 to 5, wherein the
quaternizing agent is a compound of the general formula 2
R.sub.1OC(O)-A-C(O)OR.sub.1a (2) in which R.sub.1 and R.sub.1a are
each independently a lower alkyl radical and A is an optionally
mono- or polysubstituted hydrocarbylene such as, more particularly,
an optionally mono- or polysubstituted alkylene or alkenylene.
8. The use according to any of claims 1 to 5, wherein the
quaternizing agent comprises an epoxide of the general formula 4
##STR00005## where the R.sub.d radicals present therein are the
same or different and are each H or a hydrocarbyl radical, where
the hydrocarbyl radical is an aliphatic or aromatic radical having
at least 1 to 10 carbon atoms and the free acid of the quaternizing
agent is a free protic acid, especially a C.sub.1-12-monocarboxylic
acid or -dicarboxylic acid.
9. The use according to any of the preceding claims, wherein the
quaternizable tertiary amine is a compound of the formula 3 in
which at least two of the R.sub.a, R.sub.b and R.sub.c radicals are
the same or different and are each a straight-chain or branched
C.sub.10-C.sub.20-alkyl radical and the other radical is
C.sub.1-C.sub.4-alkyl.
10. The use according to any of the preceding claims, wherein the
quaternizing agent is selected from lower alkylene oxides in
combination with a monocarboxylic acid, alkyl salicylates, dialkyl
phthalates and dialkyl oxalates.
11. The use according to any of the preceding claims, wherein the
fuel is selected from diesel fuels, biodiesel fuels, gasoline
fuels, and alkanol-containing gasoline fuels.
12. A quaternized nitrogen compound as defined in any of claims 1
to 10.
13. A process for preparing a quaternized nitrogen compound
according to claim 12, comprising the reaction of a quaternizable
alkylamine comprising at least one quaternizable tertiary amino
group with a quaternizing agent which converts the at least one
tertiary amino group to a quaternary ammonium group, the
quaternizing agent being the alkyl ester of a cycloaromatic or
cycloaliphatic mono- or polycarboxylic acid, especially of a mono-
or dicarboxylic acid, or of an aliphatic polycarboxylic acid,
especially dicarboxylic acid, or a hydrocarbyl epoxide in
combination with an acid.
14. An additive concentrate comprising, in combination with further
diesel fuel additives or gasoline fuel additives or lubricant
additives, at least one quaternized nitrogen compound as defined in
claim 12 or prepared according to claim 13.
15. A fuel composition or lubricant composition comprising, in a
majority of a customary fuel or lubricant, a proportion of at least
one reaction product comprising a quaternized nitrogen compound, or
of a fraction thereof which comprises a quaternized nitrogen
compound and is obtained from the reaction product by purification,
said reaction product being obtainable by reacting a quaternizable
alkylamine comprising at least one quaternizable tertiary amino
group with a quaternizing agent which converts the at least one
tertiary amino group to a quaternary ammonium group, the
quaternizing agent being the alkyl ester of a cycloaromatic or
cycloaliphatic mono- or polycarboxylic acid, especially of a mono-
or dicarboxylic acid, or of an aliphatic polycarboxylic acid,
especially dicarboxylic acid, an alkyl epoxide, optionally in
combination with a free acid, or a dialkyl carbonate.
16. The fuel composition or lubricant composition according to
claim 15, wherein the alkylamine comprises at least one compound of
the following general formula 3 R.sub.aR.sub.bR.sub.cN (3) in which
at least one of the R.sub.a, R.sub.b and R.sub.c radicals is a
straight-chain or branched, saturated or unsaturated
C.sub.8-C.sub.40-hydrocarbyl radical (especially straight-chain or
branched C.sub.8-C.sub.40-alkyl) and the remaining radicals are
identical or different, straight-chain or branched, saturated or
unsaturated C.sub.1-C.sub.6-hydrocarbyl radicals (especially
C.sub.1-C.sub.6-alkyl); or in which all R.sub.a, R.sub.b and
R.sub.c radicals are identical or different, straight-chain or
branched, saturated or unsaturated C.sub.8-C.sub.40-hydrocarbyl
radicals, especially straight-chain or branched
C.sub.8-C.sub.40-alkyl radicals.
17. The fuel composition or lubricant composition according to
either of claims 15 and 16, wherein the quaternizing agent is a
compound of the general formula 1 R.sub.1OC(O)R.sub.2 (1) in which
R.sub.1 is a lower alkyl radical and R.sub.2 is an optionally
substituted monocyclic aryl or cycloalkyl radical, where the
substituent is selected from OH, NH.sub.2, NO.sub.2, C(O)OR.sub.3,
and R.sub.1OC(O)--, in which R.sub.1 is as defined above and
R.sub.3 is H or R.sub.1.
18. The fuel composition or lubricant composition according to
either of claims 15 and 16, wherein the quaternizing agent is a
compound of the general formula 2 R.sub.1OC(O)-A-C(O)OR.sub.1a (2)
in which R.sub.1 and R.sub.1a are each independently a lower alkyl
radical and A is an optionally mono- or polysubstituted
hydrocarbylene such as, more particularly, an optionally mono- or
polysubstituted alkylene or alkenylene.
19. The fuel composition or lubricant composition according to
either of claims 15 to 16, wherein the quaternizing agent comprises
an epoxide of the general formula 4 ##STR00006## where the R.sub.d
radicals present therein are the same or different and are each H
or a hydrocarbyl radical, where the hydrocarbyl radical is an
aliphatic or aromatic radical having at least 1 to 10 carbon atoms
and the free acid of the quaternizing agent is a free protic acid,
especially a C.sub.1-12-monocarboxylic acid or -dicarboxylic
acid.
20. The fuel composition or lubricant composition according to any
of claims 15 to 19, wherein the quaternizable tertiary amine is a
compound of the formula 3 in which at least two of the R.sub.a,
R.sub.b and R.sub.c radicals are the same or different and are each
a straight-chain or branched C.sub.10-C.sub.20-alkyl radical and
the other radical is C.sub.1-C.sub.4-alkyl.
21. The fuel composition or lubricant composition according to any
of claims 15 to 20, wherein the quaternizing agent is selected from
lower alkylene oxides in combination with a monocarboxylic acid,
alkyl salicylates, dialkyl phthalates and dialkyl oxalates.
22. The fuel composition or lubricant composition according to any
of the preceding claims 15 to 21, selected from diesel fuels,
biodiesel fuels, gasoline fuels, and alkanol-containing gasoline
fuels.
Description
[0001] The present invention relates to the use of quaternized
alkylamine nitrogen compounds as a fuel additive and lubricant
additive, such as, more particularly, as a detergent additive; for
reduction or prevention of deposits in the injection systems of
direct injection diesel engines, especially in common rail
injection systems, for reduction of the fuel consumption of direct
injection diesel engines, especially of diesel engines with common
rail injection systems, and for minimization of power loss in
direct injection diesel engines, especially in diesel engines with
common rail injection systems; and as an additive for gasoline
fuels, especially for operation of DISI engines.
STATE OF THE ART
[0002] In direct injection diesel engines, the fuel is injected and
distributed ultrafinely (nebulized) by a multihole injection nozzle
which reaches directly into the combustion chamber of the engine,
instead of being introduced into a prechamber or swirl chamber as
in the case of the conventional (chamber) diesel engine. The
advantage of the direct injection diesel engines lies in their high
performance for diesel engines and nevertheless low fuel
consumption. Moreover, these engines achieve a very high torque
even at low speeds.
[0003] At present, essentially three methods are being used for
injection of the fuel directly into the combustion chamber of the
diesel engine: the conventional distributor injection pump, the
pump-nozzle system (unit-injector system or unit-pump system), and
the common rail system.
[0004] In the common rail system, the diesel fuel is conveyed by a
pump with pressures up to 2000 bar into a high-pressure line, the
common rail. Proceeding from the common rail, branch lines run to
the different injectors which inject the fuel directly into the
combustion chamber. The full pressure is always applied to the
common rail, which enables multiple injection or a specific
injection form. In the other injection systems, in contrast, only
smaller variation in the injection is possible. The injection in
the common rail is divided essentially into three groups: (1.)
pre-injection, by which essentially softer combustion is achieved,
such that harsh combustion noises ("nailing") are reduced and the
engine seems to run quietly; (2.) main injection, which is
responsible especially for a good torque profile; and (3.)
post-injection, which especially ensures a low NO.sub.x value. In
this post-injection, the fuel is generally not combusted, but
instead vaporized by residual heat in the cylinder. The exhaust
gas/fuel mixture formed is transported to the exhaust gas system,
where the fuel, in the presence of suitable catalysts, acts as a
reducing agent for the nitrogen oxides NO.sub.x.
[0005] The variable, cylinder-individual injection in the common
rail injection system can positively influence the pollutant
emission of the engine, for example the emission of nitrogen oxides
(NO.sub.x), carbon monoxide (CO) and especially of particulates
(soot). This makes it possible, for example, for engines equipped
with common rail injection systems to meet the Euro 4 standard
theoretically even without additional particulate filters.
[0006] 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.
[0007] 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.
[0008] U.S. Pat. No. 4,248,719 describes quaternized ammonium salts
which are prepared by reacting an alkenylsuccinimide with a
monocarboxylic ester and find use as dispersants in lubricant oils
for prevention of sludge formation. More particularly, for example,
the reaction of polyisobutylsuccinic anhydride (PIBSA) with
N,N-dimethylaminopropylamine (DMAPA) and quaternization with methyl
salicylate is described. However, use in fuels, more particularly
diesel fuels, is not proposed therein. The use of PIBSA with low
bismaleation levels of <20% is not described therein.
[0009] U.S. Pat. No. 4,171,959 describes quaternized ammonium salts
of hydrocarbyl-substituted succinimides, which are suitable as
detergent additives for gasoline fuel compositions. Quaternization
is preferably accomplished using alkyl halides. Also mentioned are
organic C.sub.2-C.sub.8-hydrocarbyl carboxylates and sulfonates.
Consequently, the quaternized ammonium salts provided according to
the teaching therein have, as a counterion, either a halide or a
C.sub.2-C.sub.8-hydrocarbyl carboxylate or a
C.sub.2-C.sub.8-hydrocarbyl sulfonate group. The use of PIBSA with
low bismaleation levels of <20% is likewise not described
therein.
[0010] EP-A-2 033 945 discloses cold flow improvers which are
prepared by quaternizing specific tertiary monoamines bearing at
least one C.sub.8-C.sub.40-alkyl radical with a
C.sub.1-C.sub.4-alkyl ester of specific carboxylic acids. Examples
of such carboxylic esters are dimethyl oxalate, dimethyl maleate,
dimethyl phthalate and dimethyl fumarate. Uses other than that for
improvement of the CFPP value of middle distillates are not
demonstrated in EP-A-2 033 945.
[0011] WO 2006/135881 describes quaternized ammonium salts prepared
by condensation of a hydrocarbyl-substituted acylating agent and of
an oxygen or nitrogen atom-containing compound with a tertiary
amino group, and subsequent quaternization by means of hydrocarbyl
epoxide in the presence of stoichiometric amounts of an acid such
as, more particularly, acetic acid. Further quaternizing agents
claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and
hydrocarbyl-substituted carbonates, and dimethyl sulfate, benzyl
chloride and dimethyl carbonate have been studied
experimentally.
[0012] The quaternizing agents used with preference in WO
2006/135881, however, have serious disadvantages such as: toxicity
or carcinogenicity (for example in the case of dimethyl sulfate and
benzyl halides), no residue-free combustion (for example in the
case of dimethyl sulfate and alkyl halides), and inadequate
reactivity which leads to incomplete quaternization or uneconomic
reaction conditions (long reaction times, high reaction
temperatures, excess of quaternizing agent; for example in the case
of dimethyl carbonate).
[0013] EP-A-2 033 945 describes the preparation of halogen- and
sulfur-free quaternary ammonium salts of organic carboxylic acids
(for example oxalic acid, phthalic acid, salicylic acid, malonic
acid and maleic acid, and the alkyl esters thereof) and the use
thereof for improvement of the CFPP value of diesel fuels.
[0014] Quaternary ammonium salts of alpha-hydroxycarboxylic acids
are proposed in EP-A-1 254 889 as cleaning agents for electronic
components.
[0015] In addition, Japanese patent application, application number
61-012197, describes the use of quaternary ammonium salts of
organic carboxylic acids as surfactants or raw materials for
medicaments or cosmetics.
[0016] It was therefore an object of the present invention to
provide further fuel additives which prevent deposits in the
injector tip and internal injector deposits in the course of
operation of common rail diesel engines.
BRIEF DESCRIPTION OF THE INVENTION
[0017] It has now been found that, surprisingly, the above object
is achieved by providing quaternized hydrocarbylamine compounds and
fuel and lubricant compositions additized therewith.
[0018] Surprisingly, the inventive additives, as illustrated more
particularly by the appended use examples, are surprisingly
effective in common rail diesel engines and are notable for their
particular suitability as an additive for reducing power loss
resulting from external deposits and cold start problems resulting
from internal deposits.
DESCRIPTION OF FIGURES
[0019] FIG. 1 shows a measurement of the time-dependent (h) change
in the exhaust gas temperatures of the cylinders in the case of use
of a fuel without additive; large deviations in the temperature are
caused by internal injector deposits.
[0020] FIG. 2 shows the time-dependent (h) change in the exhaust
gas temperatures in the same cylinders as in FIG. 1, but now after
treatment with the inventive additive from preparation example 3,
dosage 394 mg/kg.
[0021] FIG. 3 shows the profile of a one-hour engine test cycle to
CEC F-098-08.
DETAILED DESCRIPTION OF THE INVENTION
A1) Specific Embodiments
[0022] The present invention relates especially to the following
specific embodiments: [0023] 1. A fuel composition or lubricant
composition comprising, in a majority of a customary fuel or
lubricant, a proportion, especially an effective amount, of at
least one reaction product comprising a quaternized nitrogen
compound, or a fraction thereof which comprises a quaternized
nitrogen compound and is obtained from the reaction product by
purification, said reaction product being obtainable by [0024]
reacting a quaternizable alkylamine comprising at least one
quaternizable tertiary amino group with a quaternizing agent which
converts the at least one tertiary amino group to a quaternary
ammonium group, [0025] the quaternizing agent being the alkyl ester
of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid,
especially of a mono- or dicarboxylic acid, or of an aliphatic
polycarboxylic acid, especially dicarboxylic acid, a hydrocarbyl
epoxide, optionally in combination with a free acid, or a dialkyl
carbonate such as di-C.sub.1-C.sub.4-carbonate, especially dimethyl
carbonate. [0026] 2. The fuel composition or lubricant composition
according to embodiment 1, wherein the alkylamine comprises at
least one compound of the following general formula 3
[0026] R.sub.aR.sub.bR.sub.cN (3) [0027] in which [0028] at least
one of the R.sub.a, R.sub.b and R.sub.c radicals, for example one
or two, is a straight-chain or branched, saturated or unsaturated
C.sub.8-C.sub.40-hydrocarbyl radical (especially straight-chain or
branched C.sub.8-C.sub.40-alkyl) and the remaining radicals are
identical or different, straight-chain or branched, saturated or
unsaturated C.sub.1-C.sub.6-hydrocarbyl radicals (especially
C.sub.1-C.sub.6-alkyl); or [0029] 2a. The fuel composition or
lubricant composition according to embodiment 1, wherein the
alkylamine comprises at least one compound of the following general
formula 3
[0029] R.sub.aR.sub.bR.sub.cN (3) [0030] in which all R.sub.a,
R.sub.b and R.sub.c radicals are identical or different,
straight-chain or branched, saturated or unsaturated
C.sub.8-C.sub.40-hydrocarbyl radicals, especially straight-chain or
branched C.sub.8-C.sub.40-alkyl radicals. [0031] 3. The fuel
composition or lubricant composition according to any of the
preceding embodiments, wherein the quaternizing agent is a compound
of the general formula 1
[0031] R.sub.1OC(O)R.sub.2 (1) [0032] in which [0033] R.sub.1 is a
low molecular weight hydrocarbyl radical such as alkyl or alkenyl
radical, especially a lower alkyl radical such as, more
particularly, methyl or ethyl, and [0034] R.sub.2 is an optionally
substituted monocyclic hydrocarbyl radical, especially an aryl or
cycloalkyl or cycloalkenyl radical, especially aryl such as phenyl,
where the substituent is selected from OH, NH.sub.2, NO.sub.2,
C(O)OR.sub.3, and R.sub.1OC(O)--, in which R.sub.1 is as defined
above and R.sub.3 is H or R.sub.1, where the substituent is
especially OH. More particularly, the quaternizing agent is a
phthalate or a salicylate, such as dimethyl phthalate or methyl
salicylate. [0035] 4. The fuel composition according to either of
embodiments 1 and 2, wherein the quaternizing agent is a compound
of the general formula 2
[0035] R.sub.1OC(O)-A-C(O)OR.sub.1a (2) [0036] in which [0037]
R.sub.1 and R.sub.1a are each independently a low molecular weight
hydrocarbyl radical such as an alkyl or alkenyl radical, especially
a lower alkyl radical, and [0038] A is an optionally mono- or
polysubstituted hydrocarbylene (such as, more particularly, an
optionally mono- or polysubstituted C.sub.1-C.sub.7-alkylene or
C.sub.2-C.sub.7-alkenylene); where suitable substituents, for
example, are selected from OH, NH.sub.2, NO.sub.2, or C(O)OR.sub.3,
especially OH and C(O)OR.sub.3, where R.sub.3 is as defined above.
[0039] 5. The fuel composition or lubricant composition according
to either of embodiments 1 and 2, wherein the quaternizing agent
comprises an epoxide of the general formula 4
[0039] ##STR00001## [0040] where [0041] the R.sub.d radicals
present therein are the same or different and are each H or a
hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic
or aromatic radical having at least 1 to 10 carbon atoms and the
free acid of the quaternizing agent is a free protic acid,
especially a C.sub.1-12-mono-, -di- or -oligocarboxylic acid.
[0042] 6. The fuel composition or lubricant composition according
to any of the preceding embodiments, wherein the quaternizable
tertiary amine is a compound of the formula 3 in which at least two
of the R.sub.a, R.sub.b and R.sub.c radicals are the same or
different and are each a straight-chain or branched
C.sub.10-C.sub.20-alkyl radical and the other radical is
C.sub.1-C.sub.4-alkyl. [0043] 7. The fuel composition or lubricant
composition according to any of the preceding embodiments, wherein
the quaternizing agent is selected from lower alkylene oxides in
combination with a monocarboxylic acid, alkyl salicylates, dialkyl
phthalates and dialkyl oxalates. [0044] 8. The fuel composition or
lubricant composition according to any of the preceding
embodiments, selected from diesel fuels, biodiesel fuels, gasoline
fuels, and alkanol-containing gasoline fuels, such as
bioethanol-containing fuels, especially diesel fuels. [0045] 9. A
quaternized nitrogen compound as defined in any of embodiments 1 to
7. [0046] 10. A process for preparing a quaternized nitrogen
compound according to embodiment 9, [0047] comprising the reaction
of a quaternizable alkylamine comprising at least one quaternizable
tertiary amino group with a quaternizing agent which converts the
at least one tertiary amino group to a quaternary ammonium group,
[0048] the quaternizing agent being the alkyl ester of a
cycloaromatic or cycloaliphatic mono- or polycarboxylic acid,
especially of a mono- or dicarboxylic acid, or of an aliphatic
polycarboxylic acid, especially dicarboxylic acid, or a hydrocarbyl
epoxide in combination with an acid. [0049] 11. The use of a
quaternized nitrogen compound according to embodiment 9 or prepared
according to embodiment 10 as a fuel additive or lubricant
additive. [0050] 12. The use according to embodiment 11 as an
additive for reducing the fuel consumption of direct injection
diesel engines, especially of diesel engines with common rail
injection systems, and/or for minimizing power loss in direct
injection diesel engines, especially in diesel engines with common
rail injection systems (for example determined in a DW10 test based
on CEC F-098-08, as described in detail in the experimental below).
[0051] 13. The use according to embodiment 11 as a gasoline fuel
additive for reducing the level of deposits in the intake system of
a gasoline engine, such as, more particularly, DISI and PFI (port
fuel injector) engines. [0052] 14. The use according to embodiment
10 as a diesel fuel additive for reducing and/or preventing
deposits in the injection systems, for example determined in a XUD
9 test to CEC-F-23-1-01, such as, more particularly, the internal
diesel injector deposits (IDIDs), and/or valve sticking in direct
injection diesel engines, especially in common rail injection
systems (for example determined by an IDID test procedure as
described in detail in the experimental below). [0053] 15. An
additive concentrate comprising, in combination with further diesel
fuel additives or gasoline fuel additives or lubricant additives,
at least one quaternized nitrogen compound as defined in embodiment
9 or prepared according to embodiment 10.
[0054] Test methods suitable for examination of each of the
above-designated applications are known to those skilled in the
art, or are described in the experimental which follows, to which
explicit and general reference is hereby made.
A2) General Definitions
[0055] In the absence of statements to the contrary, the following
general definitions apply:
[0056] "Hydrocarbyl" can be interpreted widely and comprises both
long-chain and short-chain, straight-chain and branched hydrocarbyl
radicals having 1 to 50 carbon atoms, which may optionally
additionally comprise heteroatoms, for example O, N, NH, S, in the
chain thereof. A specific group of hydrocarbyl radicals comprises
both long-chain and short-chain, straight-chain or branched alkyl
radicals having 1 to 50 carbon atoms.
[0057] "Long-chain" hydrocarbyl radicals are straight-chain or
branched hydrocarbyl radicals and have 7 to 50 or 8 to 50 or 8 to
40 or 10 to 20 carbon atoms, which may optionally additionally
comprise heteroatoms, for example O, N, NH, S, in the chain
thereof. In addition, the radicals may be mono- or polyunsaturated
and have one or more noncumulated, for example 1 to 5, such as 1, 2
or 3, C--C double bonds or C--C triple bonds, especially 1, 2 or 3
double bonds. They may be of natural or synthetic origin. They may
also have a number-average molecular weight (M.sub.n) of 85 to 20
000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000,
for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500.
In that case, they are more particularly formed essentially from
C.sub.2-6, especially C.sub.2-4, 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-C.sub.2-6- or
poly-C.sub.2-4-alkylene radicals. Suitable long-chain hydrocarbyl
radicals and the preparation thereof are also described, for
example, in WO 2006/135881 and the literature cited therein. A
specific group of long-chain hydrocarbyl radicals comprises
straight-chain or branched alkyl radicals ("long-chain" alkyl
radicals) having 8 to 50, for example 8 to 40 or 8 to 30 or 10 to
20, carbon atoms.
[0058] "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 --O-- or --NH--, or optionally mono-
or polysubstituted, for example di-, tri- or tetrasubstituted.
[0059] "Hydrocarbylene" represents straight-chain or singly or
multiply branched bridging groups having 1 to 10 carbon atoms,
optionally interrupted by one or more, for example 2, 3 or 4,
heteroatom groups such as --O-- or --NH--, or optionally mono- or
polysubstituted, for example di-, tri- or tetrasubstituted.
[0060] "Alkyl" or "lower alkyl" represents especially saturated,
straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to
5, 1 to 6, or 1 to 7, carbon atoms, for example methyl, ethyl,
n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,
1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,
3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; and also
n-heptyl, and the singly or multiply branched analogs thereof.
[0061] "Long-chain alkyl" especially represents saturated,
straight-chain or branched hydrocarbyl radicals having 8 to 50, for
example 8 to 40 or 8 to 30 or 10 to 20, carbon atoms, such as
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers,
especially singly or multiply branched isomers and higher homologs
thereof.
[0062] "Alkenyl" represents mono- or polyunsaturated, especially
monounsaturated, straight-chain or branched hydrocarbon radicals
having 2 to 4, 2 to 6 or 2 to 7 carbon atoms and a double bond in
any position, for example C.sub.2-C.sub.6-alkenyl such as ethenyl,
1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,
3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,
1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and
1-ethyl-2-methyl-2-propenyl.
[0063] "Alkylene" represents straight-chain or mono- or
polybranched hydrocarbon bridging groups having 1 to 10 carbon
atoms, for example C.sub.1-C.sub.1-alkylene groups selected from
--CH.sub.2--, --(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--CH.sub.2--CH(CH.sub.3)--, --CH(CH.sub.3)--CH.sub.2--,
--(CH.sub.2).sub.4--, --(CH.sub.2).sub.2--CH(CH.sub.3)--,
--CH.sub.2--CH(CH.sub.3)--CH.sub.2--, (CH.sub.2).sub.4--,
--(CH.sub.2).sub.5--, --(CH.sub.2).sub.6, --(CH.sub.2).sub.7--,
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH(CH.sub.3)-- or
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH.sub.2--CH(CH.sub.3)-- or
C.sub.1-C.sub.4-alkylene groups selected from --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--CH.sub.2--CH(CH.sub.3)--,
--CH(CH.sub.3)--CH.sub.2--, --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.2--CH(CH.sub.3)--,
--CH.sub.2--CH(CH.sub.3)--CH.sub.2--.
[0064] "Alkenylene" represents the mono- or polyunsaturated,
especially monounsaturated, analogs of the above alkylene groups
having 2 to 10 carbon atoms, especially C.sub.2-C.sub.7-alkenylenes
or C.sub.2-C.sub.4-alkenylene, such as --CH.dbd.CH--,
--CH.dbd.CH--CH.sub.2--, --CH.sub.2--CH.dbd.CH--,
--CH.dbd.CH--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.dbd.CH--CH.sub.2--,
--CH.sub.2--CH.sub.2--CH.dbd.CH--, --CH(CH.sub.3)--CH.dbd.CH--,
--CH.sub.2--C(CH.sub.3).dbd.CH--.
[0065] "Cycloalkyl" represents carbocyclic radicals having 3 to 20
carbon atoms, for example C.sub.3-C.sub.12-cycloalkyl such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl;
preference is given to cyclopentyl, cyclohexyl, cycloheptyl, and
also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl,
cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl,
cyclohexylmethyl or C.sub.3-C.sub.7-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.
[0066] "Aryl" represents mono- or polycyclic, preferably mono- or
bicyclic, optionally substituted aromatic radicals having 6 to 20,
for example 6 to 10, ring carbon atoms, for example phenyl,
biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl,
fluorenyl, indenyl and phenanthrenyl. These aryl radicals may
optionally bear 1, 2, 3, 4, 5 or 6 identical or different
substituents.
[0067] "Substituents" for radicals specified herein are especially,
unless stated otherwise, selected from keto groups, --COON,
--COO-alkyl, --OH, --SH, --CN, amino, --NO.sub.2, alkyl, or alkenyl
groups.
[0068] "Mn" represents the number-average molecular weight and is
determined in a conventional manner; more particularly, such
statements relate to Mn values determined by gel permeation
chromatography.
A3) Tertiary amines of the Formula (3)
[0069] Tertiary amines of the formula (3) are compounds known per
se, as described, for example, in EP-A-2 033 945.
[0070] The tertiary amine reactant (3) preferably bears a segment
of the formula NR.sub.a R.sub.b where one of the radicals has an
alkyl group having 8 to 40 carbon atoms and the other an alkyl
group having up to 40 and more preferably 8 to 40 carbon atoms. The
R.sub.c radical is especially a short-chain C.sub.1-C.sub.6-alkyl
radical, such as a methyl, ethyl or propyl group. R.sub.a and
R.sub.b may be straight-chain or branched, and/or may be the same
or different. For example, R.sub.a and R.sub.b may be a
straight-chain C.sub.12-C.sub.24-alkyl group. Alternatively, only
one of the two radicals may be long-chain (for example having
having 8 to 40 carbon atoms), and the other may be a methyl, ethyl
or propyl group.
[0071] Appropriately, the NR.sub.aR.sub.b segment is derived from a
secondary amine, such as dioctadecylamine, dicocoamine,
hydrogenated ditallowamine and methylbehenylamine. Amine mixtures
as obtainable from natural materials are likewise suitable. One
example is a secondary hydrogenated tallowamine where the alkyl
groups are derived from hydrogenated tallow fat, and contain about
4% by weight of C.sub.14, 31% by weight of C.sub.16 and 59% by
weight of C.sub.18-alkyl groups. Corresponding tertiary amines of
the formula (3) are sold, for example, by Akzo Nobel under the
Armeen.RTM. M2HT or Armeen.RTM. M2C name.
[0072] The tertiary amine reactant (3) may also take such a form
that the R.sub.a, R.sub.b and R.sub.c radicals have identical or
different long-chain alkyl radicals, especially straight-chain or
branched alkyl groups having 8 to 40 carbon atoms.
[0073] Further nonlimiting examples of suitable amines are:
[0074] N,N-dimethyl-N-(2-ethylhexyl)amine,
N,N-dimethyl-N-(2-propylheptyl)amine, dodecyl-dimethylamine,
hexadecyldimethylamine, oleyldimethylamine, cocoyldimethylamine,
dicocoylmethylamine, tallowedimethylamine, ditallowmethylamine,
tridodecylamine, trihexadecylamine, trioctadecylamine,
soyadimethylamine, tris(2-ethylhexyl)amine, and Alamine 336
(tri-n-octylamine).
A4) Quaternizing Agents
[0075] Useful quaternizing agents in principle include all
compounds suitable as such. The quaternizing agent is especially
selected from alkylene oxides, optionally in combination with acid;
aliphatic or aromatic carboxylic esters such as, more particularly,
dialkyl carboxylates; alkanoates; cyclic nonaromatic or aromatic
carboxylic esters; alkyl sulfates; alkyl halides; alkylaryl
halides; dialkyl carbonates; and mixtures thereof.
[0076] Suitable examples are alkyl esters, derived from carboxylic
acids, whose pK.sub.a is less than 3.5. Examples are especially
alkyl esters derived from oxalic acid, phthalic acid, salicylic
acid, maleic acid, malonic acid and citric acid.
[0077] In a particular embodiment, however, the at least one
quaternizable tertiary nitrogen atom is quaternized with at least
one quaternizing agent selected from
[0078] a) compounds of the general formula 1
R.sub.1OC(O)R.sub.2 (1)
in which R.sub.1 is a lower alkyl radical and R.sub.2 is an
optionally substituted monocyclic aryl or cycloalkyl radical, where
the substituent is selected from OH, NH.sub.2, NO.sub.2,
C(O)OR.sub.3; R.sub.1aOC(O)-- in which R.sub.1a is as defined above
for R.sub.1, and R.sub.3 is H or R.sub.1; or b) compounds of the
general formula 2
R.sub.1OC(O)-A-C(O)OR.sub.1a (2)
in which R.sub.1 and R.sub.1a are each independently a lower alkyl
radical and A is an optionally mono- or polysubstituted
hydrocarbylene (such as, more particularly, an optionally mono- or
polysubstituted C.sub.1-C.sub.7-alkylene or
C.sub.2-C.sub.7-alkenylene); where suitable substituents, for
example, are selected from OH, NH.sub.2, NO.sub.2, or C(O)OR.sub.3,
especially OH and C(O)OR.sub.3, where R.sub.3 is as defined
above.
[0079] Particularly suitable compounds of the formula 1 are those
in which
R.sub.1 is a C.sub.1-, C.sub.2- or C.sub.3-alkyl radical and
R.sub.2 is a substituted phenyl radical, where the substituent is
HO-- or an ester radical of the formula R.sub.1aOC(O)-- which is in
the para, meta or especially ortho position to the R.sub.1OC(O)--
radical on the aromatic ring.
[0080] Especially suitable quaternizing agents are the lower alkyl
esters of salicylic acid, such as methyl salicylate, ethyl
salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl
salicylate.
[0081] Abovementioned esters are typically used in the presence of
acids, especially in the presence of free protic acids such as, in
particular, with C.sub.1-12-monocarboxylic acids such as formic
acid, acetic acid or propionic acid, or C.sub.2-12-dicarboxylic
acids such as oxalic acid or adipic acid; or else in the presence
of sulfonic acids such as benzenesulfonic acid or toluenesulfonic
acid, or aqueous mineral acids such as sulfuric acid or
hydrochloric acid.
[0082] c) In a further particular embodiment, the at least one
quaternizable tertiary nitrogen atom is quaternized with at least
one quaternizing agent selected from epoxides, especially
hydrocarbyl epoxides.
##STR00002##
where the R.sub.d radicals present therein are the same or
different and are each H or a hydrocarbyl radical, where the
hydrocarbyl radical has at least 1 to 10 carbon atoms. These are
especially aliphatic or aromatic radicals, for example linear or
branched C.sub.1-10-alkyl radicals, or aromatic radicals such as
phenyl or C.sub.1-4-alkylphenyl.
[0083] Examples of suitable hydrocarbyl epoxides include aliphatic
and aromatic alkylene oxides such as, more particularly,
C.sub.2-12-alkylene oxides such as ethylene oxide, propylene oxide,
1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide
(isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide,
2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene
oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene
oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide,
1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide;
and aromatic-substituted ethylene oxides such as optionally
substituted styrene oxide, especially styrene oxide or
4-methylstyrene oxide.
[0084] In the case of use of epoxides as quaternizing agents, these
are used in the presence or in the absence of free acids,
especially in the presence or absence of free protic acids, such
as, in particular, with C.sub.1-12-monocarboxylic acids such as
formic acid, acetic acid or propionic acid, or
C.sub.2-12-dicarboxylic acids such as oxalic acid or adipic acid;
or else in the presence or absence of sulfonic acids such as
benzenesulfonic acid or toluenesulfonic acid, or aqueous mineral
acids such as sulfuric acid or hydrochloric acid. The
quaternization product thus prepared is thus either
"acid-containing" or "acid-free" in the context of the present
invention.
A5) Preparation of Inventive Additives
[0085] a) Quaternization
[0086] The quaternization is performed in a manner known per
se.
[0087] (1) To perform the quaternization, the tertiary amine is
admixed with at least one compound of the above formula 1 or 2,
especially in the stoichiometric amounts required to achieve the
desired quaternization. It is possible to use, for example, 0.1 to
5.0, 0.2 to 3.0 or 0.5 to 2.5 equivalents of quaternizing agent per
equivalent of quaternizable tertiary nitrogen atom. More
particularly, however, about 1 to 2 equivalents of quaternizing
agent are used in relation to the tertiary amine, in order to fully
quaternize the tertiary amine group.
[0088] Typical working temperatures here are in the range from 50
to 180.degree. C., for example 90 to 160.degree. C. or 100 to
140.degree. C. The reaction time may be in the region of a few
minutes or a few hours, for example about 10 minutes up to about 24
hours. The reaction can be effected at a pressure of about 0.1 to
20 bar, for example 1 to 10 or 1.5 to 3 bar, but especially at
about standard pressure.
[0089] If required, the reactants can be initially charged for the
quaternization in a suitable inert organic aliphatic or aromatic
solvent or a mixture thereof. Typical examples are, for example,
solvents of the Solvesso series, toluene or xylene, or
ethylhexanol. The quaternization can, however, also be performed in
the absence of a solvent.
[0090] To perform the quaternization, the addition of catalytically
active amounts of an acid may be appropriate. Preference is given
to aliphatic monocarboxylic acids, for example
C.sub.1-C.sub.18-monocarboxylic acids such as, more particularly,
lauric acid, isononanoic acid or 3,3,5-trimethylhexanoic acid or
neodecanoic acid, but also aliphatic dicarboxylic acids or
polybasic aliphatic carboxylic acids with a carbon atom number in
the range specified above. The quaternization can also be performed
in the presence of a Lewis acid. The quaternization can, however,
also be performed in the absence of any acid.
[0091] (2) The quaternization with an epoxide of the formula (4) is
likewise effected in a manner known per se. When the boiling
temperature of one component of the reaction mixture, especially of
the epoxide, at standard pressure is above the reaction
temperature, the reaction is appropriately performed in an
autoclave.
[0092] For example, in an autoclave, a solution of the tertiary
amine is admixed with the organic acid (for example acetic acid) in
the required stoichiometric amounts. It is possible to use, for
example, 0.1 to 2.0, 0.2 to 1.5 or 0.5 to 1.25 equivalents of acid
per equivalent of quaternizable tertiary nitrogen atom. More
particularly, however, approximately equimolar proportions of the
acid are used. This is followed by sufficient purging with N.sub.2,
and establishment of a suitable initial pressure, and metered
addition of the epoxide (e.g. propylene oxide) in the
stoichiometric amounts required at a temperature between 20.degree.
C. and 180.degree. C. It is possible to use, for example, 0.1 to
4.0, 0.2 to 3 or 0.5 to 2 equivalents of epoxide per equivalent of
quaternizable tertiary nitrogen atom. More particularly, however,
about 1 to 2 equivalents of epoxide are used in relation to the
tertiary amine, in order to fully quaternize the tertiary amine
group. This is followed by stirring over a suitably long period of
a few minutes up to about 24 hours, for example about 10 h, at a
temperature between 20.degree. C. and 180.degree. C. (e.g.
50.degree. C.), cooling, for example to about 20 to 50.degree. C.,
purging with N2 and emptying of the reactor.
[0093] The reaction can be effected at a pressure of about 0.1 to
20 bar, for example 1 to 10 or 1.5 to 5 bar. However, the reaction
can also be effected at standard pressure. An inert gas atmosphere
is particular appropriate, for example nitrogen.
[0094] If required, the reactants can be initially charged for the
quaternization in a suitable inert organic aliphatic or aromatic
solvent or a mixture thereof. Typical examples are, for example,
solvents of the Solvesso series, toluene or xylene, or
2-ethylhexanol. The quaternization can, however, also be performed
in the absence of a solvent.
[0095] The quaternization can be performed in the presence of a
protic solvent, optionally also in combination with an aliphatic or
aromatic solvent. Suitable protic solvents especially have a
dielectric constant (at 20.degree. C.) of greater than 7. The
protic solvent may comprise one or more OH groups, and may also be
water. Suitable solvents may also be alcohols, glycols and glycol
ethers. More particularly, suitable protic solvents may be those
specified in WO 2010132259. Especially suitable solvents are
methanol, ethanol, n-propanol, isopropanol, all isomers of butanol,
all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol,
2-propylheptanol, and also mixtures of different alcohols. The
presence of a protic solvent can positively influence the
conversion and the reaction rate of the quaternization.
[0096] b) Workup of the Reaction Mixture
[0097] The reaction end product thus formed can theoretically be
purified further, or the solvent can be removed. Optionally, excess
reagent, for example excess epoxide, can be removed. This can be
accomplished, for example, by introducing nitrogen at standard
pressure or under reduced pressure. In order to improve the further
processibility of the products, however, it is also possible to add
solvents after the reaction, for example solvents of the Solvesso
series, 2-ethylhexanol, or essentially aliphatic solvents. However,
this is usually not absolutely necessary, and so the reaction
product can be used without further purification as an additive,
optionally after blending with further additive components (see
below).
B) Further Additive Components
[0098] The fuel additized with the inventive quaternized additive
is a gasoline fuel or especially a middle distillate fuel, in
particular a diesel fuel.
[0099] The fuel may comprise further customary additives to improve
efficacy and/or suppress wear.
[0100] 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.
[0101] In the case of gasoline fuels, these are in particular
lubricity improvers (friction modifiers), corrosion inhibitors,
demulsifiers, dehazers, antifoams, combustion improvers,
antioxidants or stabilizers, antistats, metallocenes, metal
deactivators, dyes and/or solvents.
[0102] Typical examples of suitable coadditives are listed in the
following section:
B1) Detergent Additives
[0103] The customary detergent additives are preferably amphiphilic
substances which possess at least one hydrophobic hydrocarbon
radical with a number-average molecular weight (M.sub.n) of 85 to
20 000 and at least one polar moiety selected from: [0104] (Da)
mono- or polyamino groups having up to 6 nitrogen atoms, at least
one nitrogen atom having basic properties; [0105] (Db) nitro
groups, optionally in combination with hydroxyl groups; [0106] (Dc)
hydroxyl groups in combination with mono- or polyamino groups, at
least one nitrogen atom having basic properties; [0107] (Dd)
carboxyl groups or the alkali metal or alkaline earth metal salts
thereof; [0108] (De) sulfonic acid groups or the alkali metal or
alkaline earth metal salts thereof; [0109] (Df) polyoxy-C.sub.2- to
C.sub.4-alkylene moieties terminated by hydroxyl groups, mono- or
polyamino groups, at least one nitrogen atom having basic
properties, or by carbamate groups; [0110] (Dg) carboxylic ester
groups; [0111] (Dh) moieties derived from succinic anhydride and
having hydroxyl and/or amino and/or amido and/or imido groups;
and/or [0112] (Di) moieties obtained by Mannich reaction of
substituted phenols with aldehydes and mono- or polyamines.
[0113] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel, has a
number-average molecular weight (M.sub.n) of 85 to 20 000,
preferably of 113 to 10 000, more preferably of 300 to 5000, even
more preferably of 300 to 3000, even more especially preferably of
500 to 2500 and especially of 700 to 2500, in particular of 800 to
1500. As typical hydrophobic hydrocarbon radicals, especially in
conjunction with the polar, especially polypropenyl, polybutenyl
and polyisobutenyl radicals with a number-average molecular weight
M.sub.n of preferably in each case 300 to 5000, more preferably 300
to 3000, even more preferably 500 to 2500, even more especially
preferably 700 to 2500 and especially 800 to 1500 into
consideration.
[0114] Examples of the above groups of detergent additives include
the following:
[0115] Additives comprising mono- or polyamino groups (Da) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or on high-reactivity (i.e. having predominantly
terminal double bonds) or conventional (i.e. having predominantly
internal double bonds) polybutene or polyisobutene having
M.sub.n=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 .beta.
and .gamma. positions) are used as starting materials in the
preparation of the additives, a possible preparative route is by
chlorination and subsequent amination or by oxidation of the double
bond with air or ozone to give the carbonyl or carboxyl compound
and subsequent amination under reductive (hydrogenating)
conditions. The amines used here for the amination may be, for
example, ammonia, monoamines or the abovementioned polyamines.
Corresponding additives based on polypropene are described more
particularly in WO-A 94/24231.
[0116] Further particular additives comprising monoamino groups
(Da) are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P=5 to
100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen,
as described more particularly in WO-A 97/03946.
[0117] Further particular additives comprising monoamino groups
(Da) are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described more particularly in DE-A 196 20
262.
[0118] Additives comprising nitro groups (Db), optionally in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P=5 to
100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and oxygen, as described more particularly in WO-A 96/03367
and in WO-A 96/03479. These reaction products are generally
mixtures of pure nitropolyisobutenes (e.g.
.alpha.,.beta.-dinitropolyisobutene) and mixed
hydroxynitropolyisobutenes (e.g.
.alpha.-nitro-.beta.-hydroxypolyisobutene).
[0119] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (Dc) are especially reaction products of
polyisobutene epoxides obtainable from polyisobutene having
preferably predominantly terminal double bonds and M.sub.n=300 to
5000, with ammonia or mono- or polyamines, as described more
particularly in EP-A 476 485.
[0120] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (Dd) are preferably copolymers of
C.sub.2- to C.sub.40-olefins with maleic anhydride which have a
total molar mass of 500 to 20 000 and some or all of whose carboxyl
groups have been converted to the alkali metal or alkaline earth
metal salts and any remainder of the carboxyl groups has been
reacted with alcohols or amines. Such additives are disclosed more
particularly by EP-A 307 815. Such additives serve mainly to
prevent valve seat wear and can, as described in WO-A 87/01126,
advantageously be used in combination with customary fuel
detergents such as poly(iso)buteneamines or polyetheramines.
[0121] Additives comprising sulfonic acid groups or their alkali
metal or alkaline earth metal salts (De) are preferably alkali
metal or alkaline earth metal salts of an alkyl sulfosuccinate, as
described more particularly in EP-A 639 632. Such additives serve
mainly to prevent valve seat wear and can be used advantageously in
combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
[0122] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (Df) are preferably polyethers or polyetheramines which
are obtainable by reaction of C.sub.2- to C.sub.60-alkanols,
C.sub.6- to C.sub.30-alkanediols, mono- or di-C.sub.2- to
C.sub.30-alkylamines, C.sub.1- to C.sub.30-alkylcyclohexanols or
C.sub.1- to C.sub.30-alkylphenols with 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group and, in the case of the polyetheramines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described more particularly in EP-A
310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. In the case
of polyethers, such products also have carrier oil properties.
Typical examples thereof are tridecanol butoxylates or
isotridecanol butoxylates, isononylphenol butoxylates and also
polyisobutenol butoxylates and propoxylates, and also the
corresponding reaction products with ammonia.
[0123] Additives comprising carboxylic ester groups (Dg) are
preferably esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, especially those having a minimum
viscosity of 2 mm.sup.2/s at 100.degree. C., as described more
particularly in DE-A 38 38 918. The mono-, di- or tricarboxylic
acids used may be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, 6 to 24 carbon atoms. Typical
representatives of the esters are adipates, phthalates,
isophthalates, terephthalates and trimellitates of isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products also
satisfy carrier oil properties.
[0124] 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 M.sub.n=preferably 300 to
5000, more preferably 300 to 3000, even more preferably 500 to
2500, even more especially preferably 700 to 2500 and especially
800 to 1500, with maleic anhydride by a thermal route in an ene
reaction or via the chlorinated polyisobutene. The moieties having
hydroxyl and/or amino and/or amido and/or imido groups are, for
example, carboxylic acid groups, acid amides of monoamines, acid
amides of di- or polyamines which, in addition to the amide
function, also have free amine groups, succinic acid derivatives
having an acid and an amide function, carboximides with monoamines,
carboximides with di- or polyamines which, in addition to the imide
function, also have free amine groups, or diimides which are formed
by the reaction of di- or polyamines with two succinic acid
derivatives. In the presence of imido moieties D(h), the further
detergent additive in the context of the present invention is,
however, used only up to a maximum of 100% of the weight of
compounds with betaine structure. Such fuel additives are common
knowledge and are described, for example, in documents (1) and (2).
They are preferably the reaction products of alkyl- or
alkenyl-substituted succinic acids or derivatives thereof with
amines and more preferably the reaction products of
polyisobutenyl-substituted succinic acids or derivatives thereof
with amines. Of particular interest in this context are reaction
products with aliphatic polyamines (polyalkyleneimines) such as
especially ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine
and hexaethyleneheptamine, which have an imide structure.
[0125] Additives comprising moieties (Di) obtained by Mannich
reaction of substituted phenols with aldehydes and mono- or
polyamines are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or
polyamines such as ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols
may originate from conventional or high-reactivity polyisobutene
having M.sub.n=300 to 5000. Such "polyisobutene Mannich bases" are
described more particularly in EP-A 831 141.
[0126] 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
[0127] Carrier oils additionally used may be of mineral or
synthetic nature. Suitable mineral carrier oils are the fractions
obtained in crude oil processing, such as brightstock or base oils
having viscosities, for example, from the SN 500-2000 class; but
also aromatic hydrocarbons, paraffinic hydrocarbons and
alkoxyalkanols. Likewise useful is a fraction which is obtained in
the refining of mineral oil and is known as "hydrocrack oil"
(vacuum distillate cut having a boiling range of from about 360 to
500.degree. C., obtainable from natural mineral oil which has been
catalytically hydrogenated under high pressure and isomerized and
also deparaffinized). Likewise suitable are mixtures of the
abovementioned mineral carrier oils.
[0128] Examples of suitable synthetic carrier oils are polyolefins
(polyalphaolefins or polyinternalolefins), (poly)esters,
(poly)alkoxylates, polyethers, aliphatic polyetheramines,
alkylphenol-started polyethers, alkylphenol-started polyetheramines
and carboxylic esters of long-chain alkanols.
[0129] Examples of suitable polyolefins are olefin polymers having
M.sub.n=400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or unhydrogenated).
[0130] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2- to
C.sub.4-alkylene moieties which are obtainable by reacting C.sub.2-
to C.sub.60-alkanols, C.sub.6- to C.sub.30-alkanediols, mono- or
di-C.sub.2- to C.sub.30-alkylamines, C.sub.1- to
C.sub.30-alkylcyclohexanols or C.sub.1- to C.sub.30-alkylphenols
with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or
butylene oxide per hydroxyl group or amino group, and, in the case
of the polyetheramines, by subsequent reductive amination with
ammonia, monoamines or polyamines. Such products are described more
particularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4
877 4,877,416. For example, the polyetheramines used may be
poly-C.sub.2- to C.sub.6-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.
[0131] Examples of carboxylic esters of long-chain alkanols are
more particularly esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described more particularly in
DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; particularly suitable ester alcohols
or ester polyols are long-chain representatives having, for
example, 6 to 24 carbon atoms. Typical representatives of the
esters are adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di(n- or isotridecyl) phthalate.
[0132] 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.
[0133] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having about 5 to 35, preferably about 5
to 30, more preferably 10 to 30 and especially 15 to 30 C.sub.3- to
C.sub.6-alkylene oxide units, for example propylene oxide,
n-butylene oxide and isobutylene oxide units, or mixtures thereof,
per alcohol molecule. Nonlimiting examples of suitable starter
alcohols are long-chain alkanols or phenols substituted by
long-chain alkyl in which the long-chain alkyl radical is
especially a straight-chain or branched C.sub.6- to C.sub.18-alkyl
radical. Particular examples include tridecanol and nonylphenol.
Particularly preferred alcohol-started polyethers are the reaction
products (polyetherification products) of monohydric aliphatic
C.sub.6- to C.sub.18-alcohols with C.sub.3- to C.sub.6-alkylene
oxides. Examples of monohydric aliphatic C.sub.6-C.sub.18-alcohols
are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol,
decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol,
tetradecanol, pentadecanol, hexadecanol, octadecanol and the
constitutional and positional isomers thereof. The alcohols can be
used either in the form of the pure isomers or in the form of
technical grade mixtures. A particularly preferred alcohol is
tridecanol. Examples of C.sub.3- to C.sub.6-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 C.sub.3- to C.sub.4-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.
[0134] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A 10 102 913.
[0135] Particular carrier oils are synthetic carrier oils,
particular preference being given to the above-described
alcohol-started polyethers.
[0136] The carrier oil or the mixture of different carrier oils is
added to the fuel in an amount of preferably 1 to 1000 ppm by
weight, more preferably of 10 to 500 ppm by weight and especially
of 20 to 100 ppm by weight.
B3) Cold Flow Improvers
[0137] Suitable cold flow improvers are in principle all organic
compounds which are capable of improving the flow performance of
middle distillate fuels or diesel fuels under cold conditions. For
the intended purpose, they must have sufficient oil solubility.
More particularly, useful cold flow improvers for this purpose are
the cold flow improvers (middle distillate flow improvers, MDFIs)
typically used in the case of middle distillates of fossil origin,
i.e. in the case of customary mineral diesel fuels. However, it is
also possible to use organic compounds which partly or
predominantly have the properties of a wax antisettling additive
(WASA) when used in customary diesel fuels. They can also act
partly or predominantly as nucleators. It is also possible to use
mixtures of organic compounds effective as MDFIs and/or effective
as WASAs and/or effective as nucleators.
[0138] The cold flow improver is typically selected from
(K1) copolymers of a C.sub.2- to C.sub.40-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.
[0139] 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).
[0140] Suitable C.sub.2- to C.sub.40-olefin monomers for the
copolymers of class (K1) are, for example, those having 2 to 20 and
especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2
carbon-carbon double bonds, especially having one carbon-carbon
double bond. In the latter case, the carbon-carbon double bond may
be arranged either terminally .alpha.-olefins) or internally.
However, preference is given to .alpha.-olefins, particular
preference to .alpha.-olefins having 2 to 6 carbon atoms, for
example propene, 1-butene, 1-pentene, 1-hexene and in particular
ethylene.
[0141] 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.
[0142] When further olefins are also copolymerized, they are
preferably higher in molecular weight than the abovementioned
C.sub.2- to C.sub.40-olefin base monomer. When, for example, the
olefin base monomer used is ethylene or propene, suitable further
olefins are especially C.sub.10- to C.sub.40-.alpha.-olefins.
Further olefins are in most cases only additionally copolymerized
when monomers with carboxylic ester functions are also used.
[0143] Suitable (meth)acrylic esters are, for example, esters of
(meth)acrylic acid with C.sub.1- to C.sub.20-alkanols, especially
C.sub.1- to C.sub.10-alkanols, 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.
[0144] Suitable alkenyl carboxylates are, for example, C.sub.2- to
C.sub.14-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 .alpha. position to the carboxyl group, and the
.alpha.-carbon atom is more preferably tertiary, i.e. the
carboxylic acid is what is called a neocarboxylic acid. However,
the hydrocarbon radical of the carboxylic acid is preferably
linear.
[0145] 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.
[0146] Ethylene-vinyl acetate copolymers usable particularly
advantageously and the preparation thereof are described in WO
99/29748.
[0147] 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.
[0148] Terpolymers of a C.sub.2- to C.sub.40-.alpha.-olefin, a
C.sub.1- to C.sub.20-alkyl ester of an ethylenically unsaturated
monocarboxylic acid having 3 to 15 carbon atoms and a C.sub.2- to
C.sub.14-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.
[0149] 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 C.sub.2- to C.sub.40 base olefins.
[0150] The copolymers of class (K1) preferably have a
number-average molecular weight M.sub.n of 1000 to 20 000, more
preferably of 1000 to 10 000 and especially of 1000 to 8000.
[0151] 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 .alpha.-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 .alpha.-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.
[0152] 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
U.S. Pat. No. 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.
[0153] Polar nitrogen compounds suitable as components of class
(K4) may be either ionic or nonionic and preferably have at least
one substituent, especially at least two substituents, in the form
of a tertiary nitrogen atom of the general formula>NR.sup.7 in
which R.sup.7 is a C.sub.8- to C.sub.40-hydrocarbyl radical. The
nitrogen substituents may also be quaternized, i.e. be in cationic
form. An example of such nitrogen compounds is that of ammonium
salts and/or amides which are obtainable by the reaction of at
least one amine substituted by at least one hydrocarbon radical
with a carboxylic acid having 1 to 4 carboxyl groups or with a
suitable derivative thereof. The amines preferably comprise at
least one linear C.sub.8- to C.sub.40-alkyl radical. Primary amines
suitable for preparing the polar nitrogen compounds mentioned are,
for example, octylamine, nonylamine, decylamine, undecylamine,
dodecylamine, tetradecylamine and the higher linear homologs;
secondary amines suitable for this purpose are, for example,
dioctadecylamine and methylbehenylamine. Also suitable for this
purpose are amine mixtures, especially amine mixtures obtainable on
the industrial scale, such as fatty amines or hydrogenated
tallamines, as described, for example, in Ullmann's Encyclopedia of
Industrial Chemistry, 6th Edition, "Amines, aliphatic" chapter.
Acids suitable for the reaction are, for example,
cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic
acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic
acid, phthalic acid, isophthalic acid, terephthalic acid, and
succinic acids substituted by long-chain hydrocarbon radicals.
[0154] More particularly, the component of class (K4) is an
oil-soluble reaction product of poly(C.sub.2- to
C.sub.20-carboxylic acids) having at least one tertiary amino group
with primary or secondary amines. The poly(C.sub.2- to
C.sub.20-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.
[0155] The component of class (K4) is preferably an oil-soluble
reaction product based on poly(C.sub.2- to C.sub.20-carboxylic
acids) which have at least one tertiary amino group and are of the
general formula IIa or IIb
##STR00003##
in which the variable A is a straight-chain or branched C.sub.2- to
C.sub.6-alkylene group or the moiety of the formula III
##STR00004##
and the variable B is a C.sub.1- to C.sub.19-alkylene group. The
compounds of the general formulae IIa and IIb especially have the
properties of a WASA.
[0156] Moreover, the preferred oil-soluble reaction product of
component (K4), especially that of the general formula IIa or IIb,
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.
[0157] Straight-chain or branched C.sub.2- to C.sub.6-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-dimethyl-1,3-propylene, 1,6-hexylene
(hexamethylene) and especially 1,2-ethylene. The variable A
comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.
[0158] C.sub.1- to C.sub.19-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.
[0159] 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.
[0160] These parent amines of the oil-soluble reaction products of
component (K4) are usually secondary amines and have the general
formula HN(R.sup.8).sub.2 in which the two variables R.sup.8 are
each independently straight-chain or branched C.sub.10- to
C.sub.30-alkyl radicals, especially C.sub.14- to C.sub.24-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 acids and from
derivatives thereof. The two R.sup.8 radicals are preferably the
same.
[0161] 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.
[0162] Typical examples of such components (K4) are reaction
products of nitrilotriacetic acid, of ethylenediaminetetraacetic
acid or of propylene-1,2-diaminetetraacetic acid with in each case
0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per
carboxyl group, of dioleylamine, dipalmitamine, dicocoamine,
distearylamine, dibehenylamine or especially ditallowamine. A
particularly preferred component (K4) is the reaction product of 1
mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated
ditallowamine.
[0163] Further typical examples of component (K4) include the
N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for
example the reaction product of 1 mol of phthalic anhydride and 2
mol of ditallowamine, the latter being hydrogenated or
unhydrogenated, and the reaction product of 1 mol of an
alkenylspirobislactone with 2 mol of a dialkylamine, for example
ditallowamine and/or tallowamine, the latter two being hydrogenated
or unhydrogenated.
[0164] Further typical structure types for the component of class
(K4) are cyclic compounds with tertiary amino groups or condensates
of long-chain primary or secondary amines with carboxylic
acid-containing polymers, as described in WO 93/18115.
[0165] Sulfocarboxylic acids, sulfonic acids or derivatives thereof
suitable as cold flow improvers of the component of class (K5) are,
for example, the oil-soluble carboxamides and carboxylic esters of
ortho-sulfobenzoic acid, in which the sulfonic acid function is
present as a sulfonate with alkyl-substituted ammonium cations, as
described in EP-A 261 957.
[0166] Poly(meth)acrylic esters suitable as cold flow improvers of
the component of class (K6) are either homo- or copolymers of
acrylic and methacrylic esters. Preference is given to copolymers
of at least two different (meth)acrylic esters which differ with
regard to the esterified alcohol. The copolymer optionally
comprises another different olefinically unsaturated monomer in
copolymerized form. The weight-average molecular weight of the
polymer is preferably 50 000 to 500 000. A particularly preferred
polymer is a copolymer of methacrylic acid and methacrylic esters
of saturated C.sub.14- and 015' alcohols, the acid groups having
been neutralized with hydrogenated tallamine. Suitable
poly(meth)acrylic esters are described, for example, in WO
00/44857.
[0167] The cold flow improver or the mixture of different cold flow
improvers is added to the middle distillate fuel or diesel fuel in
a total amount of preferably 10 to 5000 ppm by weight, more
preferably of 20 to 2000 ppm by weight, even more preferably of 50
to 1000 ppm by weight and especially of 100 to 700 ppm by weight,
for example of 200 to 500 ppm by weight.
B4) Lubricity Improvers
[0168] 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 U.S.
Pat. No. 6,743,266 B2, of natural or synthetic oils, for example
triglycerides, and alkanolamines are also suitable as such
lubricity improvers.
B5) Corrosion Inhibitors
[0169] 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
[0170] 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/PO block copolymers, polyethyleneimines or else
polysiloxanes.
B7) Dehazers
[0171] 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
[0172] 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
[0173] 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
[0174] 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
[0175] Suitable metal deactivators are, for example, salicylic acid
derivatives such as N,N'-disalicylidene-1,2-propanediamine.
B12) Solvents
[0176] Suitable solvents are, for example, nonpolar organic
solvents such as aromatic and aliphatic hydrocarbons, for example
toluene, xylenes, white spirit and products sold under the trade
names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil),
and also polar organic solvents, for example, alcohols such as
[0177] 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
[0178] The inventive additive is outstandingly suitable as a fuel
additive and can be used in principle in any fuels. It brings about
a whole series of advantageous effects in the operation of internal
combustion engines with fuels. Preference is given to using the
inventive quaternized additive in middle distillate fuels,
especially diesel fuels.
[0179] 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.
[0180] 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.degree. C. These are usually
distillates having a 95% point up to 360.degree. C. or even higher.
These may also be what is called "ultra low sulfur diesel" or "city
diesel", characterized by a 95% point of, for example, not more
than 345.degree. C. and a sulfur content of not more than 0.005% by
weight or by a 95% point of, for example, 285.degree. 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.
[0181] 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
A12, p. 617 ff.).
[0182] In addition to the use thereof in the abovementioned middle
distillate fuels of fossil, vegetable or animal origin, which are
essentially hydrocarbon mixtures, the inventive quaternized
additive can also be used in mixtures of such middle distillates
with biofuel oils (biodiesel). Such mixtures are also encompassed
by the term "middle distillate fuel" in the context of the present
invention. They are commercially available and usually comprise the
biofuel oils in minor amounts, typically in amounts of 1 to 30% by
weight, especially of 3 to 10% by weight, based on the total amount
of middle distillate of fossil, vegetable or animal origin and
biofuel oil.
[0183] 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
C.sub.1-C.sub.4-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").
[0184] 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.
[0185] 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.
[0186] 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.
[0187] The invention is now illustrated in detail by the working
examples which follow. Especially the test methods specified
hereinafter form part of the general disclosure of the application
and are not restricted to the specific working examples.
EXPERIMENTAL
[0188] Reagents Used:
[0189] N-methyl-N,N-ditallowamine: Armeen.RTM. M2HT from Akzo
Nobel, CAS 61788-63-4, total amine value 103-110 mg KOH/g. [0190]
Solvent Naphtha Heavy from Exxon Mobil, CAS 64742-94-5. [0191]
dimethyl oxalate from Aldrich, CAS 553-90-2 [0192] lauric acid from
Aldrich, CAS 143-07-7 [0193] 3,5,5-trimethylhexanoic acid from
BASF, CAS 3302-10-1 [0194] methyl salicylate from Aldrich, CAS
119-36-8 [0195] 2-ethylhexanol from BASF, CAS 104-76-7 [0196]
acetic acid from Aldrich, CAS 64-19-7
A. General Test Methods
[0197] Engine Test
[0198] 1. XUD9 Test--Determination of Flow Restriction
[0199] The procedure was according to the standard stipulations of
CEC F-23-1-01.
[0200] 2. DW10 Test--Determination of Power Loss as a Result of
Injector Deposits in the Common Rail Diesel Engine
[0201] 2.1. DW10-KC--Keep-Clean Test
[0202] The keep-clean test is based on CEC test procedure F-098-08
Issue 5. This is done using the same test setup and engine type
(PEUGEOT DW10) as in the CEC procedure.
[0203] Change and Special Features:
[0204] In the tests, cleaned injectors were used. The cleaning time
in the ultrasound bath in water+10% Superdecontamine
(Intersciences, Brussels) at 60.degree. C. was 4 h.
[0205] Test Run Times:
[0206] The test run time was 12 h without shutdown phases. The
one-hour test cycle from CEC F-098-08, shown in FIG. 2, was run
through 12 times.
[0207] Performance Determination:
[0208] The initial power P0,KC [kW] is calculated from the measured
torque at full load 4000/min directly after the test has started
and the engine has run hot. The procedure is described in Issue 5
of the test procedure (CEC F-98-08). This is done using the same
test setup and the PEUGEOT DW10 engine type.
[0209] The final performance (Pend,KC) is determined in the 12th
cycle in stage 12 (see table, FIG. 2). Here too, the operation
point is full load 4000/min. Pend,KC [kW] is calculated from the
torque measured.
[0210] The power loss in the KC test is calculated as follows:
Powerloss , KC [ % ] = ( 1 - Pend , KC P 0 , KC ) * 100
##EQU00001##
[0211] 2.2. DW10 Dirty-Up Clean-Up (DU-CU)
[0212] The DU-CU test is based on CEC test procedure F-098-08 Issue
5. The procedure is described in Issue 5 of the test procedure (CEC
F-98-08). This is done using the same test setup and the PEUGEOT
DW10 engine type.
[0213] The DU-CU test consists of two individual tests which are
run in succession. The first test serves to form deposits (DU), the
second to remove the deposits (CU). After the DU, the power loss is
determined. After the end of the DU run, the engine is not operated
for at least 8 hours and is cooled to ambient temperature.
Thereafter, the CU fuel is used to start the CU without
deinstalling and cleaning the injectors. The deposits and power
loss ideally decline over the course of the CU test.
[0214] Change and Special Features:
[0215] Cleaned injectors were installed in the engine prior to each
DU test. The cleaning time in the ultrasound bath at 60.degree. C.,
in water+10% Superdecontamine (Intersciences, Brussels), was 4
h.
[0216] Test Run Times:
[0217] The test run time was 12 h for the DU and 12 h for the CU.
The engine was operated in the DU and CU tests without shutdown
phases.
[0218] The one-hour test cycle from CEC F-098-08, shown in FIG. 2,
was run through 12 times in each case.
[0219] Performance Determination:
[0220] The initial power P0,du [kW] is calculated from the measured
torque at full load 4000/min directly after the test has started
and the engine has run hot. The procedure is likewise described in
Issue 5 of the test procedure.
[0221] The final performance (Pend,du) is determined in the 12th
cycle in stage 12 (see table above). Here too, the operation point
is full load 4000/min. Pend,du [kW] is calculated from the torque
measured.
[0222] The power loss in the DU is calculated as follows:
Powerloss , du [ % ] = ( 1 - Pend , du P 0 , du ) * 100
##EQU00002##
[0223] Clean-Up
[0224] The initial power P0,cu [kW] is calculated from the measured
torque at full load 4000/min directly after the test has started
and the engine has run hot in the CU. The procedure is likewise
described in Issue 5 of the test procedure.
[0225] The final performance (Pend,cu) is determined in the 12th
cycle in stage 12 (see table, FIG. 2). Here too, the operation
point is full load 4000/min. Pend,cu [kW] is calculated from the
torque measured.
[0226] The power loss in the CU test is calculated as follows
(negative number for the power loss in the CU test means an
increase in performance)
Powerloss ( DU , CU ) [ % ] = ( 1 - Pend , du - pend , cu P 0 , du
) * 100 ##EQU00003##
[0227] The fuel used was a commercial diesel fuel from Halternann
(RF-06-03). To artificially induce the formation of deposits at the
injectors, 1 ppm by weight of zinc in the form of a zinc
didodecanoate solution was added thereto.
[0228] 3. IDID Test--Determination of Additive Action Against
Internal Injector Deposits
[0229] The formation of deposits within the injector was
characterized on the basis of the deviations in the exhaust gas
temperatures of the cylinders at the cylinder outlet when the DW10
engine is cold-started.
[0230] To promote the formation of deposits, 1 mg/l of sodium salt
of an organic acid, 20 mg/l of dodecenylsuccinic acid and 10 mg/l
of water were added to the fuel.
[0231] The test is conducted as a dirty-up clean-up test
(DU-CU).
[0232] DU-CU is based on CEC test procedure F-098-08 Issue 5.
[0233] The DU-CU test consists of two individual tests which are
run in succession. The first test serves to form deposits (DU), the
second to remove the deposits (CU).
[0234] After the DU run, after a rest phase of at least eight
hours, a cold start of the engine is conducted, followed by idling
for 10 minutes.
[0235] Thereafter, the CU fuel is used to start the CU without
deinstalling and cleaning the injectors. After the CU run over 8 h,
after a rest phase of at least eight hours, a cold start of the
engine is conducted, followed by idling for 10 minutes. The
evaluation is effected by the comparison of the temperature
profiles for the individual cylinders after the cold start in the
DU and CU runs.
[0236] The IDID test indicates the formation of internal deposits
in the injector. The characteristic used in this test is the
exhaust gas temperature of the individual cylinders. In an injector
system without IDIDs, the exhaust gas temperatures of the cylinders
increase homogeneously. In the presence of IDIDs, the exhaust gas
temperatures of the individual cylinders do not increase
homogeneously and deviate from one another.
[0237] The temperature sensors are beyond the cylinder head outlet
in the exhaust gas manifold. Significant deviation of the
individual cylinder temperatures (e.g. >20.degree. C.) indicates
the presence of internal injector deposits (IDIDs).
[0238] The tests (DU and CU) are each conducted with run time 8 h.
The one-hour test cycle from CEC F-098-08 (see FIG. 3) is run
through 8 times in each case. In the event of deviations of the
individual cylinder temperatures of greater than 45.degree. C. from
the mean for all 4 cylinders, the test is stopped early.
[0239] Alteration and special features: cleaned injectors were
installed prior to the start of each DU test. The cleaning time in
the ultrasound bath at 60.degree. C., water+10% Superdecontamine,
was 4 h.
B. Preparation Examples
Preparation Example 1
N,N-dimethyl-N,N-ditallowammonium methyloxalate was Synthesized on
the Basis of EP 2 033 945
[0240] N-Methyl-N,N-ditallowamine (90 g) is admixed with dimethyl
oxalate (90 g) and lauric acid (1.8 g). The reaction mixture is
heated to 120.degree. C. and stirred at this temperature for 4 h.
Subsequently, excess dimethyl oxalate is removed at 130.degree. C.
under reduced pressure with the aid of a rotary evaporator. This
gives 110.8 g of the product as a white wax. .sup.1H NMR
(CDCl.sub.3) confirms the quaternization.
Preparation Example 2
N,N-dimethyl-N,N-ditallowammonium salicylate
[0241] N-Methyl-N,N-ditallowamine (80 g) is admixed with methyl
salicylate (45.4 g) and 3,5,5-trimethylhexanoic acid (0.8 g). The
reaction mixture is heated to 160.degree. C. and stirred at this
temperature for 4 h. After cooling to room temperature, 124 g of
the product are obtained as a white wax. .sup.1H NMR (CDCl.sub.3)
confirms the quaternization.
Preparation example 3
N-methyl-N-(2-hydroxypropyl)-N,N-ditallowammonium acetate
[0242] In a 2 l autoclave, a solution of N-methyl-N,N-ditallowamine
(250 g) in 2-ethylhexanol (250 g) is admixed with acetic acid
(100%, 33.5 g). This is followed by purging three times with
N.sub.2, establishment of an initial pressure of approx. 1.3 bar of
N2 and an increase in the temperature to 50.degree. C. Propylene
oxide (54 g) is metered in such that the temperature remains
between 45-55.degree. C. This is followed by stirring at 50.degree.
C. for 10 h, cooling to 25.degree. C., purging with N2 and emptying
of the reactor. The product is degassed on a rotary evaporator at
80.degree. C. and 20 mbar for 3 h. This gives 549.4 g of the
product in 2-ethylhexanol. .sup.1H NMR (CDCl.sub.3) confirms the
quaternization. The sample is adjusted to an active ingredient
content of 38% by addition of Solvent Naphtha Heavy.
C. Use Examples
[0243] In the use examples which follow, the additives are used
either as a pure substance (as synthesized in the above preparation
examples) or in the form of an additive package.
Use Example 1
Determination of Additive Action on the Formation of Deposits in
Diesel Engine Injection Nozzles
[0244] a) XUD9 Tests
[0245] Fuel used: RF-06-03 (reference diesel, Halternann Products,
Hamburg)
[0246] The results are summarized in table 1.
TABLE-US-00001 TABLE 1 Results of the XUD9 tests Flow restriction
Dosage 0.1 mm needle Ex. Reference ppm active stroke [%] #1
according to 30 8.4 preparation example 1 #2 according to 15 22.4
preparation example 1
[0247] b) DW10 Test
[0248] The table below shows the results of the determinations of
the relative power loss at 4000 rpm after 12 hours of sustained
operation without interruption. The value PO gives the power after
10 minutes and the value Pend the power at the end of the
measurement:
[0249] The test results are shown in table 2.
TABLE-US-00002 TABLE 2 Results of the DW10 test Dose Power loss
Power loss Power loss Additive [mg/kg] KC DU DU-CU base value 0
4.1% according to preparation 100 0.4% example 1, keep clean
according to preparation 100 -4.9% example 1, clean-up base value 0
3.8% according to preparation 100 -0.4% example 2, keep clean
[0250] It is found that the inventive additives according to
preparation examples 1 and 2 have improved action compared to the
base value.
[0251] c) Action Against Internal Injector Deposits (IDID)
[0252] Fuel used: RF-06-03 (reference diesel, Halternann Products,
Hamburg)
[0253] The test results are shown in appended FIGS. 1 and 2.
[0254] FIG. 1 shows a measurement of the exhaust gas temperatures
of the cylinders in the case of use of a fuel without additive;
large deviations in the temperature are caused by internal injector
deposits.
[0255] FIG. 2 shows the exhaust gas temperatures measured in the
same cylinders after treatment with the inventive additive from
preparation example 3, dosage 394 mg/kg.
[0256] The measurements illustrate the action of the inventive
additive for dissolution of internal injector deposits. The falls
in the exhaust gas temperature caused by the internal injector
deposits (FIG. 1, cylinders 1 and 4) can be eliminated again by the
inventive additive.
[0257] Reference is made explicitly to the disclosure of the
publications cited herein.
* * * * *