U.S. patent application number 14/062320 was filed with the patent office on 2015-04-30 for use of a complex ester to reduce fuel consumption.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Muriel Ecormier, Bjoern Thomas Hahn, Markus Hansch, Thomas Hayden, Dirk Rettemeyer, Ludwig Voelkel, Marc Walter.
Application Number | 20150113864 14/062320 |
Document ID | / |
Family ID | 51786939 |
Filed Date | 2015-04-30 |
United States Patent
Application |
20150113864 |
Kind Code |
A1 |
Walter; Marc ; et
al. |
April 30, 2015 |
USE OF A COMPLEX ESTER TO REDUCE FUEL CONSUMPTION
Abstract
The use of a complex ester obtainable by esterification reaction
between aliphatic linear or branched C.sub.2- to
C.sub.12-dicarboxylic acids, aliphatic linear or branched
polyhydroxy alcohols with 3 to 6 hydroxyl groups, and, as chain
stopping agents, aliphatic linear or branched C.sub.1- to
C.sub.30-monocarboxylic acids or aliphatic linear or branched
monobasic C.sub.1- to C.sub.30-alcohols, as an additive in a fuel
for reducing fuel consumption in the operation of an internal
combustion engine with this fuel.
Inventors: |
Walter; Marc; (Frankenthal,
DE) ; Rettemeyer; Dirk; (Hueckelhoven, DE) ;
Hansch; Markus; (Speyer, DE) ; Voelkel; Ludwig;
(Limburgerhof, DE) ; Hahn; Bjoern Thomas;
(Duesseldorf, DE) ; Ecormier; Muriel; (Mannheim,
DE) ; Hayden; Thomas; (Wappingers Falls, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
51786939 |
Appl. No.: |
14/062320 |
Filed: |
October 24, 2013 |
Current U.S.
Class: |
44/398 |
Current CPC
Class: |
C10L 10/04 20130101;
C10L 2270/023 20130101; C10M 129/78 20130101; C10L 1/1915 20130101;
C10N 2030/06 20130101; C10L 1/1608 20130101; C10N 2070/00 20130101;
C10L 10/18 20130101; C10L 2200/0423 20130101; C10M 2207/30
20130101; C10L 1/2383 20130101; C10L 10/08 20130101; C10L 2230/22
20130101; C10L 1/22 20130101; C10L 1/18 20130101; C10L 1/2222
20130101 |
Class at
Publication: |
44/398 |
International
Class: |
C10L 1/19 20060101
C10L001/19 |
Claims
1. A process for reducing fuel consumption in the operation of an
internal combustion engine, the process comprising operating an
internal combustion engine with a fuel comprising an additive
comprising a complex ester obtained by an esterification reaction
among (A) at least one aliphatic linear or branched C.sub.2- to
C.sub.12-dicarboxylic acid, (B) at least one aliphatic linear or
branched polyhydroxy alcohol having 3 to 6 hydroxyl groups, and (C)
as a chain stopping agent (C1) at least one aliphatic linear or
branched C.sub.1- to C.sub.30-monocarboxylic acid in case of an
excess of component (B), or (C2) at least one aliphatic linear or
branched monobasic C.sub.1- to C.sub.30-alcohol in case of an
excess of component (A).
2. The process of claim 1, which reduces power loss in the internal
combustion engine, and which improves acceleration of the internal
combustion engine.
3. The process of claim 1, wherein the additive is present in the
fuel in an amount effective to improve a lubricity of a lubricant
oil in the internal combustion engine.
4. The process of claim 1, wherein component (A) comprises an
aliphatic linear C.sub.6- to C.sub.10-dicarboxylic acid.
5. The process of claim 1, wherein component (B) comprises at least
one member selected from the group consisting of glycerin,
trimethylolpropane and pentaerythritol.
6. The process of claim 1, wherein component (C) comprises an
aliphatic linear or branched C.sub.8- to C.sub.18-monocarboxylic as
(C1), or comprises a linear or branched C.sub.8- to
C.sub.18-alkanol as (C2).
7. The process of claim 1, wherein the complex ester of comprises
from 2 to 9 molecule units of component (A) and comprises from 3 to
10 molecule units of component (B), wherein component (B) is in
excess compared to component (A), and remaining free hydroxyl
groups of (B) are completely or partly capped with a corresponding
number of molecule units of component (C1).
8. The process of claim 1, wherein the complex ester comprises from
3 to 10 molecule units of component (A) and comprises from 2 to 9
molecule units of component (B), wherein component (A) is in excess
compared to component (B), and remaining free carboxyl groups of
(A) are completely or partly capped with a corresponding number of
molecule units of component (C2).
9. A fuel composition comprising: in a major amount, a gasoline
fuel; in a minor amount, at least one complex ester obtained by an
esterification reaction among (A) at least one aliphatic linear or
branched C.sub.2- to C.sub.12-dicarboxylic acid, (B) at least one
aliphatic linear or branched polyhydroxy alcohol having 3 to 6
hydroxyl groups, and (C) as a chain stopping agent (C1) at least
one aliphatic linear or branched C.sub.1- to
C.sub.30-monocarboxylic acid in case of an excess of component (B),
or (C2) at least one aliphatic linear or branched monobasic
C.sub.1- to C.sub.30-alcohol in case of an excess of component (A);
and at least one fuel additive which is different from the complex
esters ester and has a detergent action.
10. The fuel composition of claim 9 comprising as the fuel additive
which is different from the complex ester at least one member (D)
selected from the group consisting of: (Da) a mono- or polyamino
group having up to 6 nitrogen atoms, at least one nitrogen atom
having basic properties; (Db) a nitro group, optionally in
combination with a hydroxyl group; (Dc) a hydroxyl group in
combination with a mono- or polyamino group, at least one nitrogen
atom having basic properties; (Dd) a carboxyl group or its alkali
metal or alkaline earth metal salt; (De) a sulfonic acid group or
its alkali metal or alkaline earth metal salt; (Df) a
polyoxy-C.sub.2-C.sub.4-alkylene moiety terminated by a hydroxyl
group, a mono- or polyamino group, at least one nitrogen atom
having basic properties, or by a carbamate group; (Dg) a carboxylic
ester group; (Dh) a moiety derived from succinic anhydride and
having a hydroxyl and/or an amino and/or an amido and/or an imido
group; and (Di) a moiety obtained by Mannich reaction of a
substituted phenol with an aldehyde and a mono- or polyamine.
11. The fuel composition of claim 9, additionally comprising, as a
further fuel additive in a minor amount, at least one carrier
oil.
12. The fuel composition of claim 9, additionally comprising, as a
further fuel additive in a minor amount, at least one tertiary
hydrocarbyl amine of formula NR.sup.1R.sup.2R.sup.3 wherein
R.sup.1, R.sup.2 and R.sup.3 are the same or different C.sub.1- to
C.sub.20-hydrocarbyl residues with the proviso that the overall
number of carbon atoms in formula NR.sup.1R.sup.2R.sup.3 does not
exceed 30.
13. The fuel composition of claim 9, comprising at least one
representative (D) that is (Da) a polyisobutene monoamine or a
polyisobutene polyamine having M.sub.n=300 to 5000, having at least
50 mol-% of vinylidene double bonds and having been prepared by
hydroformylation of a respective polyisobutene and subsequent
reductive amination with ammonia, a monoamine or a polyamine, in
combination with at least one mineral or synthetic carrier oil.
14. An additive concentrate comprising: at least one complex ester
obtained by an esterification reaction among (A) at least one
aliphatic linear or branched C.sub.2- to C.sub.12-dicarboxylic
acid, (B) at least one aliphatic linear or branched polyhydroxy
alcohol having 3 to 6 hydroxyl groups, and (C) as a chain stopping
agent (C1) at least one aliphatic linear or branched C.sub.1- to
C.sub.30-monocarboxylic acid in case of an excess of component (B),
or (C2) at least one aliphatic linear or branched monobasic
C.sub.1- to C.sub.30-alcohol in case of an excess of component (A);
and at least one fuel additive which is different from the complex
ester and has a detergent action.
15. The additive concentrate of claim 14, comprising at least one
representative (D) that is (Da) a polyisobutene monoamine or a
polyisobutene polyamine having M.sub.n=300 to 5000, having at least
50 mol-% of vinylidene double bonds and having been prepared by
hydroformylation of a respective polyisobutene and subsequent
reductive amination with ammonia, a monoamine or a polyamine, and
further comprising at least one mineral or synthetic carrier oil.
Description
[0001] The present invention relates to the use of a complex ester
obtainable by an esterification reaction between
[0002] (A) at least one aliphatic linear or branched C.sub.2- to
C.sub.12-dicarboxylic acid,
[0003] (B) at least one aliphatic linear or branched polyhydroxy
alcohol with 3 to 6 hydroxyl groups, and
[0004] (C) as a chain stopping agent [0005] (C1) at least one
aliphatic linear or branched C.sub.1- to C.sub.30-monocarboxylic
acid in case of an excess of component (B), or [0006] (C2) at least
one aliphatic linear or branched monobasic C.sub.1- to
C.sub.30-alcohol in case of an excess of component (A), as an
additive in a fuel for different purposes.
[0007] The present invention further relates to a fuel composition
which comprises a gasoline fuel, the complex ester mentioned and at
least one fuel additive with detergent action.
[0008] The present invention further relates to an additive
concentrate which comprises the complex ester mentioned and at
least one fuel additive with detergent action.
[0009] It is known that particular substances in the fuel reduce
internal friction in the internal combustion engines, especially in
gasoline engines, and thus help to save fuel. Such substances are
also referred to as lubricity improvers, friction reducers or
friction modifiers. Lubricity improvers customary on the market for
gasoline fuels are usually condensation products of naturally
occurring carboxylic acids such as fatty acids with polyols such as
glycerol or with alkanolamines, for example glyceryl
monooleate.
[0010] A disadvantage of the prior art lubricity improvers
mentioned is poor miscibility with other typically used fuel
additives, especially with detergent additives such as
polyisobuteneamines and/or carrier oils such as polyalkylene
oxides. An important requirement in practice is that the component
mixtures or additive concentrates provided are readily pumpable
even at relatively low temperatures, especially at outside winter
temperatures of, for example, down to -20.degree. C., and remain
homogene-ously stable over a prolonged period, i.e. no phase
separation and/or precipitates may occur.
[0011] Typically, the miscibility problems outlined are avoided by
adding relatively large amounts of mixtures of paraffinic or
aromatic hydrocarbons with alcohols such as tert-butanol or
2-ethylhexanol as solubilizers to the component mixtures or
additive concentrates. In some cases, however, considerable amounts
of these expensive solubilizers are necessary in order to achieve
the desired homogeneity, and so this solution to the problem
becomes uneconomic.
[0012] In addition, the prior art lubricity improvers mentioned
often have the tendency to form emulsions with water in the
component mixtures or additive concentrates or in the fuel itself,
such that water which has penetrated can be removed again via a
phase separa-tion only with difficulty or at least only very
slowly.
[0013] WO 99/16849 discloses a complex ester resulting from an
esterification reaction between polyfunctional alcohols and
polyfunctional carboxylic acids using a chain stopping agent to
form ester bonds with the remaining hydroxyl or carboxyl groups,
containing as a polyfunctional carboxylic acid component dimerised
and/or trimerised fatty acids. This complex ester is recommended
for as an additive, a base fluid or a thickener in transmission
oils, hydraulic fluids, four-stroke oils, fuel additives,
com-pressor oils, greases, chain oils and for metal working rolling
applications.
[0014] WO 98/11178 discloses a polyol ester distillate fuel
additive synthesized from a polyol an a mono- or polycarboxylic
acid in such a manner that the resulting ester has uncon-erted
hydroxyl groups, such polyol ester being useful as a lubricity
additive for diesel fuel, jet fuel and kerosene.
[0015] WO 03/012015 discloses an additive for improving the
lubricity capacity of low-sulphur fuel oils, such additive
containing an ester of a bivalent or polyvalent alcohol and a
mixture of unsaturated or saturated mono- or dicarboxylic acids
whose carbon length are between 8 and 30 carbon atoms.
[0016] It was an object of the present invention to provide fuel
additives which firstly bring about effective fuel saving in the
operation of a spark-ignited internal combustion engine, and
secondly no longer have the outlined shortcomings of the prior art,
i.e. more particularly not remaining homogeneously stable over a
prolonged period without any phase separation and/or precipitates,
poor miscibility with other fuel additives and the tendency to form
emulsions with water. In addition, they should not worsen the high
level of intake valve cleanliness achieved by the modern fuel
additives.
[0017] Accordingly, the use of a complex ester as described above
as an additive in a fuel for reducing fuel consumption in the
operation of an internal combustion engine with this fuel has been
found. Preferably, the said use as an additive in a gasoline fuel
for reducing fuel consumption in the operation of a spark-ignited
internal combustion engine with this fuel or as an additive in a
gasoline fuel for reduction of fuel consumption in the operation of
a self-ignition internal combustion engine with this fuel has been
found.
[0018] It can be assumed that the cause of the fuel saving by
virtue of the complex ester mentioned is based substantially on the
effect thereof as an additive which reduces internal friction in
the internal combustion engines, especially in gasoline engines.
The reaction product mentioned thus functions in the context of the
present invention essentially as a lubricity improver.
[0019] Furthermore, the use of a complex ester as described above
as an additive in a fuel for minimization of power loss in internal
combustion engines and for improving accelera-tion of internal
combustion engines has been found.
[0020] Furthermore, the use of a complex ester as described above
as an additive in a fuel for improving the lubricity of lubricant
oils contained in an internal combustion engine for lubricating
purposes by operating the internal combustion engine with a fuel
containing an effective amount of at least one of the said complex
esters has been found.
[0021] It can be assumed that a part of the complex ester mentioned
contained in the fuel is transported via the combustion chamber
where the additive containing fuel is burnt into the lubricant oils
and acting there as a further lubricating agent. The advantage of
this mechanism is that the said further lubricating agent is
continuously refreshed by the fuel feeding.
[0022] Spark-ignition internal combustion engines are preferably
understood to mean gasoline engines, which are typically ignited
with spark plugs. In addition to the customary four- and two-stroke
gasoline engines, spark-ignition internal combustion engines also
in-clude other engine types, for example the Wankel engine. These
are generally engines which are operated with conventional gasoline
types, especially gasoline types accor-ding to EN 228,
gasoline-alcohol mixtures such as Flex fuel with 75 to 85% by
volume of ethanol, liquid pressure gas ("LPG") or compressed
natural gas ("CNG") as fuel.
[0023] However, the inventive use of the complex ester mentioned
also relates to newly devel-oped internal combustion engines such
as the "HCCl" engine, which is self-igniting and is operated with
gasoline fuel.
[0024] The instant invention works preferably with direct injection
gasoline driven combustion engines.
[0025] The aliphatic dicarboxylic acids of component (A) may be
branched or preferably linear; they may be unsaturated or
preferably saturated. Typical examples for component (A) are
ethanedioic acid (oxalic acid), propanedioic acid (malonic acid),
butanedioic acid (succinic acid), (Z)-butenedioic acid (maleic
acid), (E)-butenedioic acid (fumaric acid), pentanedioic acid
(glutaric acid), pent-2-enedioic acid (glutaconic acid),
hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid),
octanedioic acid (suberic acid), nonanedioic acid (azelaic acid),
decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic
acid, dodec-2-enedioic acid (traumatic acid) and
(2E,4E)-hexa-2,4-dienedioic acid (muconic acid). Mixture of the
above aliphatic dicarboxylic acids can also be used.
[0026] In a preferred embodiment, the at least one aliphatic
dicarboxylic acid of component (A) is selected from aliphatic
linear C.sub.6- to C.sub.10-dicarboxylic acids which are preferably
saturated. Most preferred are adipic acid and sebacic acid.
[0027] The aliphatic polyhydroxy alcohols of component (B) may be
branched or linear; they may be unsaturated or preferably
saturated; they may contain of form 3 to 12, preferably of from 3
to 8, especially of from 3 to 6 carbon atoms and preferably 3, 4 or
5 hydroxyl groups. Typical examples for component (B) are
trimethylolethane, trimethylol-propane, trimethylolbutane,
sorbitol, glycerin and pentaerythritol. Mixtures of the above
aliphatic polyhydroxy alcohols can also be used.
[0028] In a preferred embodiment, the at least one aliphatic
polyhydroxy alcohol of component (B) is selected from glycerin,
trimethylolpropane and pentaerythritol.
[0029] Depending whether component (B) is used for the
esterification reaction in an excess compared with component (A),
resulting in remaining free hydroxyl groups, or component (A) is
used for the esterification reaction in an excess compared with
component (B), resulting in remaining free carboxylic groups, chain
stopping agent (C1) or (C2) is used for the synthesis of the
complex ester mentioned. Carboxylic ester component (C1) will
transform remaining free hydroxyl groups into additional carboxylic
ester groups. Monobasic alcohol component (C2) will transform
remaining free carboxylic groups into additional carboxylic ester
groups.
[0030] The aliphatic monocarboxylic acids of component (C1) may be
branched or linear; they may be unsaturated or preferably
saturated. Typical examples for component (A) are formic acid,
acetic acid, propionic acid, 2,2-dimethyl propionic acid
(neopentanoic acid), hexanoic acid, octanoic acid (caprylic acid),
2-ethylhexanoic acid, 3,5,5-trimethyl hexanoic acid, nonanoic acid,
decanoic acid (capric acid), undecanoic acid, dodecanoic acid
(lauric acid), tridecanoic acid, tetradecanoic acid (myristic
acid), hexadecanoic acid (palmitic acid), octadecanoic acid
(stearic acid), isostearic acid, oleic acid, linoleic acid,
linolaidic acid, erucic acid, arachidic acid, behenic acid,
lignoceric acid and cerotic acid. The above monocarboxylic acids,
including the so called fatty acids, may be of synthetic or of
natural origin. Mixtures of the above aliphatic monocarboxylic
acids can also be used.
[0031] In a preferred embodiment, the at least one aliphatic
monocarboxylic acid of component (C1) is selected from aliphatic
linear or branched C.sub.8- to C.sub.18-monocarboxylic acids.
[0032] The aliphatic monobasic alcohols of component (C2) may be
branched or linear; they may be unsaturated or preferably
saturated. Typical examples for component (C2) are methanol,
ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol,
sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol,
n-octanol, 2-ethyihexanol, n-nonanol, 2-propylheptanol, n-decanol,
n-undecanol, n-dodecanol, n-tridecanol, iso-tridecanol,
n-tetradecanol, iso-tetradecanol, n-hexadecanol, n-octadecanol,
iso-octadecanol and n-eicosanol. Mixtures of the above monobasic
alcohols can also be used. The said monobasic alcohols may have
been alkoxylated by means of hydrocarbyl epoxides like ethylene
oxide, propylene oxide and/or butylene oxide resulting in
monocapped polyethers before being used as chain stopping agents
for preparing the complex esters mentioned.
[0033] In a preferred embodiment, the at least one aliphatic
monobasic alcohol of component (C2) is selected from linear or
branched C.sub.8- to C.sub.18-alkanols.
[0034] The synthesis of the complex ester mentioned is in principle
known in the art. In more detail, it can be prepared by mixing and
reacting component (A) with (B) and subsequently reacting the
intermediate ester formed by (A) and (B) with component (C). As an
alternative, it can also be prepared by mixing an reacting
components (A), (B) and (C) simultaneously.
[0035] The complex ester mentioned is normally composed of at least
2 molecule units of component (A), at least 3 molecule units of
component (B) and the corresponding number of molecule units of
chain stopping agent (C), or of at least 2 molecule units of
component (B), at least 3 molecule units of component (A) and the
corresponding number of molecule units of chain stopping agent
(C).
[0036] In a preferred embodiment, the complex ester mentioned is
composed of from 2 to 9 molecule units, especially of from 2 to 5
molecule units of component (A) and of from 3 to 10 molecule units,
especially of from 3 to 6 molecule units of component (B),
component (B) being in excess compared with component (A), with
remaining free hydroxyl groups of (B) being completely or partly
capped with a corresponding number of molecule units of component
(C1).
[0037] In another preferred embodiment, the complex ester mentioned
is composed of from 3 to 10 molecule units, especially of from 3 to
6 molecule units of component (A) and of from 2 to 9 molecule
units, especially of from 2 to 5 molecule units of component (B),
component (A) being in excess compared with component (B), with
remaining free carboxyl groups of (A) being completely or partly
capped with a corresponding number of molecule units of component
(C2).
[0038] A typical complex ester useful for the instant invention is
composed of 3 or 4 molecule units of component (A), especially of
at least one aliphatic linear C.sub.6- to C.sub.10-dicarboxylic
acid such as adipic acid and/or sebacic acid, of 4 or 5 molecule
units of component (B), especially of glycerin, trimethylolpropane
and/or pentaerythritol, and of 6 to 12 molecule units of component
(C1), especially of at least one aliphatic linear or branched
C.sub.8- to C.sub.18-monocarboxylic acid such as octanoic acid,
2-ethylhexanoic acid, 3,5,5-trimethyl hexanoic acid, nonanoic acid,
decanoic acid and/or isostearic acid.
[0039] The complex ester mentioned is oil soluble, which means
that, when mixed with mineral oils and/or fuels in a weight ratio
of 10:90, 50:50 and 90:10, the complex ester does not show phase
separation after standing for 24 hours at room temperature for at
least two weight rations out of the three weight ratios 10:90,
50:50 and 90:10.
[0040] The present invention also provides a fuel composition which
comprises, in a major amount, a gasoline fuel and, in a minor
amount, at least one complex ester mentioned, and at least one fuel
additive which is different from the said complex esters and has
detergent action.
[0041] Typically, the amount of this at least one complex ester in
the gasoline fuel is 10 to 5000 ppm by weight, more preferably 20
to 2000 ppm by weight, even more preferably 30 to 1000 ppm by
weight and especially 40 to 500 ppm by weight, for example 50 to
300 ppm by weight.
[0042] Useful gasoline fuels include all conventional gasoline fuel
compositions. A 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. In addition, in the context of the
present invention, gasoline fuels shall also be understood to mean
alcohol-containing gasoline fuels, especially ethanol-containing
gasoline fuels, as described, for example, in WO 2004/090079, for
example Flex fuel with an ethanol content of 75 to 85% by volume,
or gasoline fuel comprising 85% by volume of ethanol ("E85"), but
also the "E100" fuel type, which is typically azeotropi-cally
distilled ethanol and thus consists of approx. 96% by volume of
C.sub.2H.sub.5OH and approx. 4% by volume of H.sub.2O.
[0043] The complex ester mentioned may be added to the particular
base fuel either alone or in the form of fuel additive packages
(for gasoline fuels also called "gasoline per-formance packages).
Such packages are fuel additive concentrates and generally also
comprise, as well as solvents, and as well as the at least one fuel
additive which is different from the said complex esters and has
detergent action, a series of further components as coadditives,
which are especially carrier oils, corrosion inhibitors,
demulsifiers, dehazers, antifoams, combustion improvers,
antioxidants or stabilizers, antistats, metallocenes, metal
deactivators, solubilizers, markers and/or dyes.
[0044] Detergents or detergent additives as the at least one fuel
additive which is different from the said complex esters and has
detergent action, referred to hereinafter as component (D),
typically refer to deposition inhibitors for fuels. The detergent
additives are preferably amphiphilic substances which possess at
least one hydrophobic hydrocarbyl radical having a number-average
molecular weight (M.sub.n) of 85 to 20 000, especially of 300 to
5000, in particular of 500 to 2500, and at least one polar
moiety.
[0045] In a preferred embodiment, the inventive fuel composition
comprises, as the at least one fuel additive (D) which is different
from the said complex esters and has detergent action, at least one
representative which is selected from:
[0046] (Da) mono- or polyamino groups having up to 6 nitrogen
atoms, at least one nitrogen atom having basic properties;
[0047] (Db) nitro groups, optionally in combination with hydroxyl
groups;
[0048] (Dc) hydroxyl groups in combination with mono- or polyamino
groups, at least one nitrogen atom having basic properties;
[0049] (Dd) carboxyl groups or their alkali metal or alkaline earth
metal salts;
[0050] (De) sulfo groups or their alkali metal or alkaline earth
metal salts;
[0051] (Df) polyoxy-C.sub.2-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;
[0052] (Dg) carboxylic ester groups;
[0053] (Dh) moieties derived from succinic anhydride and having
hydroxyl and/or amino and/or amido and/or imido groups; and/or
[0054] (Di) moieties obtained by Mannich reaction of substituted
phenols with aldehydes and mono- or polyamines.
[0055] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel
composition, has a number-average molecular weight (M.sub.n) of 85
to 20 000, especially of 300 to 5000, in particular of 500 to 2500.
Useful typical hydrophobic hydrocarbyl radicals, especially in
conjunction with the polar moieties (Da), (Dc), (Dh) and (Di), are
relatively long-chain alkyl or alkenyl groups, especially the
polypropenyl, polybutenyl and polyisobutenyl radicals each having
M.sub.n=300 to 5000, especially 500 to 2500, in particular 700 to
2300.
[0056] Examples of the above groups of detergent additives include
the following:
[0057] Additives comprising mono- or polyamino groups (Da) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or on highly-reactive (i.e. having predominantly
terminal double bonds in the .alpha.- and/or .beta.-position such
as vinylidene double bonds) or conventional (i.e. having
predominantly internal double bonds) polybutene or polyisobutene
having Mn=300 to 5000. Such detergent additives based on
highly-reactive polybutene or polyisobutene, which are normally
prepared by hydroformylation of the poly(iso)butene and subsequent
reductive amination with ammonia, monoamines or polyamines, are
known from EP-A 244 616. When the preparation of the additives
proceeds from polybutene or polyisobutene having predominantly
internal double bonds (usually in the .beta.- and/or .gamma.-
positions), one 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 polyamines such as dimethylaminopropylamine,
ethylenediamine, diethylenetriamine, triethylenetetramine or
tetraethylenepentamine. Corresponding additives based on
polypropene are described in particular in WO-A-94/24231.
[0058] Further preferred additives comprising monoamino groups (Da)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P=5 to
100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen,
as described in particular in WO-A-97/03946.
[0059] Further preferred additives comprising monoamino groups (Da)
are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described in particular in DE-A-196 20
262.
[0060] Additives comprising nitro groups (Db), optionally in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P =5
to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and oxygen, as described in particular in WO-A-96/03367 and
in WO-A 96/03479. These reaction products are generally mixtures of
pure nitropolyisobutenes (e.g. .alpha.,.beta.-dinitropolyisobutene)
and mixed hydroxynitropolyisobutenes (e.g.
.alpha.-nitro-.beta.-hydroxypolyisobutene).
[0061] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (Dc) are in particular reaction products
of polyisobutene epoxides obtainable from polyisobutene having
preferably predominantly terminal double bonds and M.sub.n=300 to
5000, with ammonia or mono- or polyamines, as described in
particular in EP-A-476 485.
[0062] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (Dd) are preferably copolymers of
C.sub.2-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 in
particular by EP-A-307 815. Such additives serve mainly to prevent
valve seat wear and can, as described in WO-A-87/01126,
advantageously be used in combination with customary fuel
detergents such as poly(iso)buteneamines or polyetheramines.
[0063] Additives comprising sulfo groups or their alkali metal or
alkaline earth metal salts (De) are preferably alkali metal or
alkaline earth metal salts of an alkyl sulfosuccinate, as described
in particular in EP-A-639 632. Such additives serve mainly to
prevent valve seat wear and can be used advantageously in
combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
[0064] 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-C.sub.60-alkanols,
C.sub.6-C.sub.30-alkane-diols, mono- or di-C2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-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 in particular in EP-A-310 875, EP-A-356 725,
EP-A-700 985 and U.S. Pat. No. 4 877 416. In the case of
polyethers, such products also have carrier oil properties. Typical
examples of these are tridecanol butoxylates, isotridecanol
butoxylates, isononyl-phenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0065] Additives comprising carboxylic ester groups (Dg) are
preferably esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, in particular those having a
minimum viscosity of 2 mm.sup.2/s at 100.degree. C., as described
in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic
acids used may be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, 6 to 24 carbon atoms. Typical
representatives of the esters are adipates, phthalates,
isophthalates, terephthalates and trimellitates of isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products also
have carrier oil properties.
[0066] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
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=300 to 5000 with maleic anhydride by a
thermal route or via the chlorinated polyisobutene. Of particular
interest in this context are derivatives with aliphatic polyamines
such as ethylenediamine, diethylenetriamine, triethylenetetramine
or tetraethylenepentamine. 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. Such fuel
additives are described especially in U.S. Pat. No. 4,849,572.
[0067] The detergent additives from group (Dh) are preferably the
reaction products of alkyl- or alkenyl-substituted succinic
anhydrides, especially of polyisobutenylsuccinic anhydrides
("PIBSAs"), with amines and/or alcohols. These are thus derivatives
which are derived from alkyl-, alkenyl- or polyisobutenylsuccinic
anhydride and have amino and/or amido and/or imido and/or hydroxyl
groups. It is self-evident that these reaction products are
obtainable not only when substituted succinic anhydride is used,
but also when substituted succinic acid or suitable acid
derivatives, such as succinyl halides or succinic esters, are
used.
[0068] The additized fuel may comprise at least one detergent based
on a polyisobutenyl-substituted succinimide. Especially of interest
are the imides with aliphatic polyamines. Particularly preferred
polyamines are ethylenediamine, diethylenetriamine,
triethylenetetramine, pentaethylenehexamine and in particular
tetraethylenepentamine. The polyisobutenyl radical has a
number-average molecular weight M.sub.n of preferably from 500 to
5000, more preferably from 500 to 2000 and in particular of about
1000.
[0069] 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 especially in EP-A-831 141.
[0070] The inventive fuel composition comprises the at least one
fuel additive which is different from the complex ester mentioned
and has detergent action, and is normally selected from the above
groups (Da) to (Di), in an amount of typically 10 to 5000 ppm by
weight, more preferably of 20 to 2000 ppm by weight, even more
preferably of 30 to 1000 ppm by weight and especially of 40 to 500
ppm by weight, for example of 50 to 250 ppm by weight.
[0071] The detergent additives (D) mentioned are preferably used in
combination with at least one carrier oil. In a preferred
embodiment, the inventive fuel composition comprises, in addition
to the at least one inventive reaction product and the at least one
fuel additive which is different than the inventive reaction
product and has detergent action, as a further fuel additive in a
minor amount, at least one carrier oil.
[0072] 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 abovementioned
mineral carrier oils.
[0073] Examples of suitable synthetic carrier oils are selected
from: polyolefins (poly-alpha-olefins or poly(internal olefin)s),
(poly)esters, (poly)alkoxylates, polyethers, aliphatic
polyetheramines, alkylphenol-started polyethers,
alkylphenol-started polyetheramines and carboxylic esters of
long-chain alkanols.
[0074] Examples of suitable polyolefins are olefin polymers having
M.sub.n=from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or unhydrogenated).
[0075] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyetheramines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyether-amines used may be
poly-C.sub.2-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.
[0076] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; suitable ester alcohols or polyols are
in particular long-chain representatives having, for example, from
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.
[0077] 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-0
452 328 and EP-A-0 548 617.
[0078] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having from about 5 to 35, for example
from about 5 to 30, C.sub.3-C.sub.6-alkylene oxide units, for
example selected from propylene oxide, n-butylene oxide and
isobutylene oxide units, or mixtures thereof. Nonlimiting examples
of suitable starter alcohols are long-chain alkanols or phenols
substituted by long-chain alkyl in which the long-chain alkyl
radical is in particular a straight-chain or branched
C.sub.6-C.sub.16-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0079] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-101 02 913.
[0080] Preferred carrier oils are synthetic carrier oils,
particular preference being given to poly-ethers.
[0081] When a carrier oil is used in addition, it is added to the
inventive additized fuel in an amount of preferably from 1 to 1000
ppm by weight, more preferably from 10 to 500 ppm by weight and in
particular from 20 to 100 ppm by weight.
[0082] In a preferred embodiment, the inventive fuel composition
comprises, in addition to the at least one inventive reaction
product, the at least one fuel additive which is different from the
complex ester mentioned and has detergent action, and optionally
the at least one carrier oil, as a further fuel additive in a minor
amount at least one tertiary hydrocarbyl amine of formula
NR.sup.1R.sup.2R.sup.3 wherein R.sup.1, R.sup.2 and R.sup.3 are the
same or different C.sub.1- to C.sub.20-hydrocarbyl residues with
the proviso that the overall number of carbon atoms in formula
NR.sup.1R.sup.2R.sup.3 does not exceed 30.
[0083] Tertiary hydrocarbyl amines have proven to be advantageous
with regard to use as performance additives in fuels controlling
deposits. Besides their superior performance behavior, they are
also good to handle as their melting points are normally low enough
to be usually liquid at ambient temperature.
[0084] "Hydrocarbyl residue" for R.sup.1 to R.sup.3 shall mean a
residue which is essentially composed of carbon and hydrogen,
however, it can contain in small amounts heteroatomes, especially
oxygen and/or nitrogen, and/or functional groups, e.g. hydroxyl
groups and/or carboxylic groups, to an extent which does not
distort the predominantly hydrocarbon character of the residue.
Hydrocarbyl residues are preferably alkyl, alkenyl, alkinyl,
cycloalkyl, aryl, alkylaryl or arylalkyl groups. Especially
preferred hydrocarbyl residues for R.sup.1 to R.sup.3 are linear or
branched alkyl or alkenyl groups.
[0085] The overall number of carbon atoms in the tertiary
hydrocarbyl amine mentioned is at most 30, preferably at most 27,
more preferably at most 24, most preferably at most 20. Preferably,
the minimum overall number of carbon atoms in formula
NR.sup.1R.sup.2R.sup.3 is 6, more preferably 8, most preferably 10.
Such size of the tertiary hydrocarbyl amine mentioned corresponds
to molecular weight of about 100 to about 450 for the largest range
and of about 150 to about 300 for the smallest range; most usually,
tertiary hydrocarbyl amines mentioned within a molecular range of
from 100 to 300 are used.
[0086] The three C.sub.1- to C.sub.20-hydrocarbyl residues may be
identical or different. Preferably, they are different, thus
creating an amine molecular which exhibits an oleophobic moiety
(i.e. the more polar amino group) and an oleophilic moiety (i.e. a
hydrocarbyl residue with a longer chain length or a larger volume).
Such amine molecules with oleophobic/oleophilic balance have proved
to show the best deposit control performance according the present
invention.
[0087] Preferably, a tertiary hydrocarbyl amine of formula
NR.sup.1R.sup.2R.sup.3 is used wherein at least two of hydrocarbyl
residues R.sup.1, R.sup.2 and R.sup.3 are different with the
proviso that the hydrocarbyl residue with the most carbon atoms
differ in carbon atom number from the hydrocarbyl residue with the
second most carbon atoms in at least 3, preferably in at least 4,
more preferably in at least 6, most preferably in at least 8. Thus,
the tertiary amines mentioned exhibit hydrocarbyl residues of two
or three different chain length or different volume,
respectively.
[0088] Still more preferably, a tertiary hydrocarbyl amine of
formula NR.sup.1R.sup.2R.sup.3 is used wherein one or two of
R.sup.1 to R.sup.3 are C.sub.7- to C.sub.20-hydrocarbyl residues
and the remaining two or one of R.sup.1 to R.sup.3 are C.sub.1- to
C.sub.4-hydrocarbyl residues.
[0089] The one or the two longer hydrocarbyl residues, which may be
in case of two residues identical or different, exhibit from 7 to
20, preferably from 8 to 18, more preferably from 9 to 16, most
preferably from 10 to 14 carbon atoms. The one or the two remaining
shorter hydrocarbyl residues, which may be in case of two residues
identical or different, exhibit from 1 to 4, preferably from 1 to
3, more preferably 1 or 2, most preferably 1 carbon atom(s).
Besides the desired deposit controlling performance, the oleophilic
long-chain hydrocarbyl residues provide further advantageous
properties to the tertiary amines, i.e. high solubility for
gasoline fuels and low volatility.
[0090] More preferably, tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are used, wherein R.sup.1 is a C.sub.8-to
C.sub.18-hydrocarbyl residue and R.sup.2 and R.sup.3 are
independently of each other C.sub.1- to C.sub.4-alkyl radicals.
Still more preferably, tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are used, wherein R.sup.1 is a C.sub.9- to
C.sub.16-hydrocarbyl residue and R.sup.2 and R.sup.3 are both
methyl radicals.
[0091] Examples for suitable linear or branched C.sub.1- to
C.sub.20-alkyl residues for R.sup.1 to R.sup.3 are: methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert-butyl,
n-pentyl, tert-pentyl, 2-methylbutyl,
3-methylbutyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, n-heptyl,
1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl,
5-methylhexyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl,
2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dime-thylpentyl,
2,5-dimethylpentyl, 2-diethylpentyl, 3-diethyl-pentyl, n-octyl,
1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl,
5-methylheptyl, 6-methylheptyl, 1,1-dimethylhexyl,
1,2-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl,
2,4-dimethyl-hexyl, 2,5-dimethylhexyl, 2,6-dimethylhexyl,
2-ethyl-hexyl, 3-ethylhexyl, 4-ethylhexyl, n-nonyl, iso-nonyl,
n-decyl, 1-propylheptyl, 2-propyl-heptyl, 3-propylheptyl,
n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and
eicosyl.
[0092] Examples for suitable linear or branched C.sub.2- to
C.sub.20-alkenyl and -alkinyl residues for R.sup.1 to R.sup.3 are:
vinyl, allyl, oleyl and propin-2-yl.
[0093] Tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 with long-chain alkyl and alkenyl residues
can also preferably be obtained or derived from natural sources,
i.e. from plant or animal oils and lards. The fatty amines derived
from such sources which are suitable as such tertiary hydro-carbyl
amines normally form mixtures of differents similar species such as
homologues, e.g. tallow amines containing as main components
tetradecyl amine, hexadecyl amine, octadecyl amine and octadecenyl
amine (oleyl amine). Further examples of suitable fatty amines are:
co-co amines and palm amines. Unsaturated fatty amines which
contain alkenyl residues can be hydrogenated and used in this
saturated form.
[0094] Examples for suitable C.sub.3- to C.sub.20-cycloalkyl
residues for R.sup.1 to R.sup.3 are: cyclopropyl, cyclobutyl,
2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,
2,3-dimethyl-cyclohexyl, 2,4-dimethylcyclohexyl,
2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl,
3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-ethylcyclohexyl,
3-ethylcyclohexyl, 4-ethylcyclohexyl, cyclooctyl and
cyclodecyl.
[0095] Examples for suitable C.sub.7- to C.sub.20-aryl, -alkylaryl
or -arylalkyl residues for R.sup.1 to R.sup.3 are: naphthyl, tolyl,
xylyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, benzyl,
1-phenyl-ethyl, 2-phenylethyl, 3-phenylpropyl and
4-butylphenyl.
[0096] Typical examples for suitable tertiary hydrocarbyl amines of
formula NR.sup.1R.sup.2R.sup.3 are the following:
[0097] N,N-dimethyl-n-butylamine, N,N-dimethyl-n-pentylamine,
N,N-dimethyl-n-hexylamine, N,N-dimethyl-n-heptylamine,
N,N-dimethyl-n-octylamine, N,N-dimethyl-2-ethylhexyl-amine,
N,N-di-methyl-n-nonylamine, N,N-dimethyl-iso-nonylamine,
N,N-dimethyl-n-decylamine, N,N-dimethyl-2-propylheptylamine,
N,N-dimethyl-n-undecylamine, N,N-dimethyl-n-dodecylamine,
N,N-dimethyl-n-tridecylamine, N,N-dimethyl-iso-tridecyl-amine,
N,N-dimethyl-n-tetradecylamine, N,N-dimethyl-n-hexadecylamine,
N,N-di-methyl-n-octadecylamine, N,N-dimethyl-eicosylamine,
N,N-dimethyl-oleylamine;
[0098] N,N-diethyl-n-heptylamine, N,N-diethyl-n-octylamine,
N,N-diethyl-2-ethylhexylamine, N,N-diethyl-n-nonylamine,
N,N-diethyl-iso-nonylamine, N,N-diethyl-n-decylamine,
N,N-diethyl-2-propylheptylamine, N,N-diethyl-n-undecylamine,
N,N-diethyl-n-dodecylamine, N,N-diethyl-n-tridecylamine,
N,N-diethyl-iso-tridecylamine, N,N-diethyl-n-tetradecyl-amine,
N,N-diethyl-n-hexadecylamine, N,N-di-ethyl-n-octadecylamine,
N,N-diethyl-eicosylamine, N,N-diethyl-oleylamine;
[0099] N,N-di-(n-propyl)-n-heptylamine,
N,N-di-(n-propyl)-n-octylamine,
N,N-di-(n-propyl)-2-ethylhexylamine,
N,N-di-(n-propyl)-n-nonylamine, N,N-di-(n-propyl)-iso-nonylamine,
N,N-di-(n-propyl)-n-decylamine,
N,N-di-(n-propyl)-2-propylheptylamine,
N,N-di-(n-propyl)-n-undecylamine, N,N-di-(n-propyl)-n-dodecylamine,
N,N-di-(n-propyl)-n-tri-decylamine,
N,N-di-(n-propyl)-iso-tridecylamine,
N,N-di-(n-propyl)-n-tetradecylamine,
N,N-di-(n-propyl)-n-hexadecylamine,
N,N-di-(n-propyl)-n-octadecylamine, N,N-di-(n-propyl)-eicosylamine,
N,N-di-(n-propyl)-oleylamine;
[0100] N,N-di-(n-butyl)-n-heptylamine,
N,N-di-(n-butyl)-n-octylamine, N,N-di-(n-butyl)-2-ethyl-hexylamine,
N,N-di-(n-butyl)-n-nonylamine, N,N-di-(n-butyl)-iso-nonylamine,
N,N-di-(n-butyI)-n- decylamine,
N,N-di-(n-butyl)-2-propylheptylamine,
N,N-di-(n-butyl)-n-undecyl-amine, N,N-di-(n-butyl)-n-dodecylamine,
N,N-di-(n-butyl)-n-tridecylamine,
N,N-di-(n-butyl)-iso-tridecylamine,
N,N-di-(n-butyl)-n-tetradecylamine,
N,N-di-(n-butyl)-n-hexa-decylamine,
N,N-di-(n-butyl)-n-octadecylamine, N,N-di-(n-butyl)-eicosylamine,
N,N-di-(n-butyl)-oleyl-amine;
[0101] N-methyl-N-ethyl-n-heptylamine,
N-methyl-N-ethyl-n-octylamine, N-methyl-N-ethyl-2-ethylhexylamine,
N-methyl-N-ethyl-n-nonylamine, N-methyl-N-ethyl-iso-nonylamine,
N-methyl-N-ethyl-n-decylamine,
N-methyl-N-ethyl-2-propylheptylamine,
N-methyl-N-ethyl-n-undecylamine, N-methyl-N-ethyl-n-dodecylamine,
N-methyl-N-ethyl-n-tridecylamine,
N-methyl-N-ethyl-iso-tridecylamine,
N-methyl-N-ethyl-n-tetradecylamine,
N-methyl-N-ethyl-n-hexadecylamine,
N-methyl-N-ethyl-n-octadecylamine, N-methyl-N-ethyl-eicosyl-amine,
N-methyl-N-ethyl-oleylamine;
[0102] N-methyl-N-(n-propyl)-n-heptylamine,
N-methyl-N-(n-propyl)-n-octylamine,
N-methyl-N-(n-propyl)-2-ethylhexylamine,
N-methyl-N-(n-propyl)-n-nonylamine,
N-methyl-N-(n-propyl)-iso-nonylamine,
N-methyl-N-(n-propyl)-n-decylamine,
N-methyl-N-(n-propyl)-2-propylheptylamine,
N-methyl-N-(n-propyl)-n-undecylamine,
N-methyl-N-(n-propyl)-n-dodecylamine,
N-methyl-N-(n-propyl)-n-tridecylamine,
N-methyl-N-(n-propyl)-iso-tri-decylamine,
N-methyl-N-(n-propyl)-n-tetradecylamine,
N-methyl-N-(n-propyl)-n-hexa-decylamine,
N-methyl-N-(n-propyl)-n-octadecylamine,
N-methyl-N-(n-propyl)-eicosyl-amine,
N-methyl-N-(n-propyl)-oleylamine;
[0103] N-methyl-N-(n-butyl)-n-heptylamine,
N-methyl-N-(n-butyl)-n-octylamine,
N-methyl-N-(n-butyl)-2-ethylhexylamine,
N-methyl-N-(n-butyl)-n-nonylamine,
N-methyl-N-(n-butyl)-iso-nonylamine,
N-methyl-N-(n-butyl)-n-decylamine,
N-methyl-N-(n-butyl)-2-propylheptyl-amine,
N-methyl-N-(n-butyl)-n-undecylamine,
N-methyl-N-(n-butyl)-n-dodecylamine,
N-methyl-N-(n-butyl)-n-tridecylamine,
N-methyl-N-(n-butyl)-iso-tridecylamine,
N-methyl-N-(n-butyl)-n-tetradecylamine,
N-methyl-N-(n-butyl)-n-hexadecylamine,
N-methyl-N-(n-butyl)-n-octadecylamine,
N-methyl-N-(n-butyl)-eicosylamine,
N-methyl-N-(n-butyl)-oleylamine;
[0104] N-methyl-N,N-di-(n-heptyl)-amine,
N-methyl-N,N-di-(n-octyl)-amine,
N-methyl-N,N-di-(2-ethylhexyl)-amine,
N-methyl-N,N-di-(n-nonyl)-amine, N-methyl-N,N-di-(iso-nonyl)-amine,
N-methyl-N, N-di-(n-decyl)-amine,
N-methyl-N,N-di-(2-propylheptyl)-amine,
N-methyl-N,N-di-(n-undecyl)-amine,
N-methyl-N,N-di-(n-dodecyl)-amine,
N-methyl-N,N-di-(n-tridecyl)-amine, N-methyl-N,
N-di-(iso-tridecyl)-amine,
N-methyl-N,N-di-(n-tetra-decyl)-amine;
[0105] N-ethyl-N,N-di-(n-heptyl)-amine,
N-ethyl-N,N-di-(n-octyl)-amine,
N-ethyl-N,N-di-(2-ethylhexyl)-amine,
N-ethyl-N,N-di-(n-nonyl)-amine, N-ethyl-N,N-di-(iso-nonyl)-amine,
N-ethyl-N,N-di-(n-decyl)-amine,
N-ethyl-N,N-di-(2-propylheptyl)-amine,
N-ethyl-N,N-di-(n-undecyl)-amine, N-ethyl-N,N-di-(n-dodecyl)-amine,
N-ethyl-N,N-di-(n-tridecyl)-amine,
N-ethyl-N,N-di-(iso-tridecyl)-amine,
N-ethyl-N,N-di-(n-tetradecyl)-amine;
N-(n-butyl)-N,N-di-(n-heptyl)-amine,
N-(n-butyl)-N,N-di-(n-octyl)-amine,
N-(n-butyl)-N,N-di-(2-ethylhexyl)-amine,
N-(n-butyl)-N,N-di-(n-nonyl)-amine,
N-(n-butyl)-N,N-di-(iso-nonyl)-amine,
N-(n-butyl)-N,N-di-(n-decyl)-amine,
N-(n-butyl)-N,N-di-(2-propylheptyl)-amine,
N-(n-butyl)-N,N-di-(n-undecyl)-amine,
N-(n-butyl)-N,N-di-(n-dodecyl)-amine,
N-(n-butyl)-N,N-di-(n-tridecyl)-amine,
N-(n-butyl)-N,N-di-(iso-tridecyl)-amine;
[0106] N-methyl-N-(n-heptyl)-N-(n-dodecyl)-amine,
N-methyl-N-(n-heptyl)-N-(n-octadecyl)-amine,
N-methyl-N-(n-octyl)-N-(2-ethylhexyl)-amine,
N-methyl-N-(2-ethylhexyl)-N-(n-dodecyl)-amine,
N-methyl-N-(2-propylheptyl)-N-(n-undecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-dodecyl)-amine,
N-methyl-N-(n-decyl)-N-(-tetradecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-hexadecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-octadecyl)-amine,
N-methyl-N-(n-decyl)-N-oleylamine,
N-methyl-N-(n-dodecyl)-N-(iso-tridecyl)-amine,
N-methyl-N-(n-dodecyl)-N-(n-tetradecyl)-amine,
N-methyl-N-(n-dodecyl)-N-(n-hexa-decyl)-amine,
N-methyl-N-(n-dodecyl)-oleylamine;
[0107] Also suitable tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are monocyclic structures, wherein one of
the short-chain hydrocarbyl residue forms with the nitrogen atom
and with the other short-chain hydrocarbyl residue a five- or
six-membered ring. Oxygen atoms and/or further nitrogen atoms may
additionally be present in such five- or six-membered ring. In each
case, such cyclic tertiary amines carry at the nitrogen atom or at
one of the nitrogen atoms, respectively, the long-chain C.sub.7- to
C.sub.20-hydrocarbyl residue. Examples for such monocyclic tertiary
amines are N-(C.sub.7- to C.sub.20-hydrocarbyl)piperidines,
N-(C.sub.7- to C.sub.20-hydrocarbyl)piperazines and N-(C.sub.7- to
C.sub.20-hydrocarbyl)morpholines.
[0108] The inventive fuel composition may comprise further
customary coadditives, as described below:
[0109] Corrosion inhibitors suitable as such coadditives are, for
example, succinic esters, in particular with polyols, fatty acid
derivatives, for example oleic esters, oligomerized fatty acids and
substituted ethanolamines.
[0110] Demulsifiers suitable as further coadditives are, for
example, the alkali metal and alkaline earth metal salts of
alkyl-substituted phenol- and naphthalenesulfonates and the alkali
metal and alkaline earth metal salts of fatty acid, and also
alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates,
e.g. tert-butylphenol ethoxylates or tert-pentylphenol ethoxylates,
fatty acid, alkylphenols, condensation products of ethylene oxide
and propylene oxide, e.g. ethylene oxide-propylene oxide block
copolymers, polyethyleneimines and polysiloxanes.
[0111] Dehazers suitable as further coadditives are, for example,
alkoxylated phenol-formal-dehyde condensates.
[0112] Antifoams suitable as further coadditives are, for example,
polyether-modified poly-siloxanes. Antioxidants suitable as further
coadditives are, for example, substituted phenols, e.g.
2,6-ditert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and
also phenylenedi-amines, e.g.
N,N'-di-sec-butyl-p-phenylenediamine.
[0113] Metal deactivators suitable as further coadditives are, for
example, salicylic acid derivatives, e.g.
N,N'-disalicylidene-1,2-propanediamine.
[0114] Suitable solvents, especially also for fuel additive
packages, are, for example, nonpolar organic solvents, especially
aromatic and aliphatic hydrocarbons, for example toluene, xylenes,
"white spirit" and the technical solvent mixtures of the
designations Shellsol.RTM. (manufacturer: Royal Dutch/Shell Group),
Exxol.RTM. (manufacturer: ExxonMobil) and Solvent Naphtha. Also
useful here, especially in a blend with the nonpolar organic
solvents mentioned, are polar organic sol-vents, in particular
alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and
2-propylheptanol.
[0115] When the coadditives and/or solvents mentioned are used in
addition in gasoline fuel, they are used in the amounts customary
therefor.
[0116] In an especially preferred embodiment, as the at least one
fuel additive (D) to be used together with the complex ester
mentioned which is different from the said complex ester and has
detergent action is selected from (Da) polyisobutene monoamines or
polyisobutene polyamines having Mn=300 to 5000, having
predominantly vinylidene double bonds (normally at least 50 mol-%
of vinylidene double bonds, especially at least 70 mol-% of
vinylidene double bonds) and having been prepared by
hydroformylation of the respective polyisobutene and subsequent
reductive amination with ammonia, monoamines or polyamines. Such
polyisobutene monoamines and polyisobutene polyamines are
preferably applied in combination with at least one mineral or
synthetic carrier oil, more preferably in combination with at least
one polyether-based or polyetheramine-based carrier oil, most
preferably in combination with at least one
C6-C.sub.18-alcohol-started polyether having from about 5 to 35
C.sub.3-C.sub.6-alkylene oxide units, especially selected from
propylene oxide, n-butylene oxide and isobutylene oxide units, as
described above.
[0117] The present invention also provides an additive concentrate
which comprises at least one complex ester mentionend, and at least
one fuel additive which is different from the said complex esters
and has detergent action. Otherwise, the inventive additive
concentrate may comprise the further coadditives mentioned above.
In case of additive concentrates for gasoline fuels, such additive
concentrates are also called gasoline performance packages.
[0118] The at least one complex ester mentioned is present in the
inventive additive concen-trate preferably in an amount of 1 to 99%
by weight, more preferably of 15 to 95% by weight and especially of
30 to 90% by weight, based in each case on the total weight of the
concentrate. The at least one fuel additive which is different from
the complex ester mentioned and has detergent action is present in
the inventive additive concentrate preferably in an amount of 1 to
99% by weight, more preferably of 5 to 85% by weight and especially
of 10 to 70% by weight, based in each case on the total weight of
the concentrate.
[0119] The complex ester mentioned mentioned provides for quite a
series of advantages and unexpected performance and handling
improvements in view of the respective solu-tions proposed in the
art. Effective fuel saving in the operation of a spark-ignited
inter-nal combustion engine is achieved. The respective fuel
additive concentrates remain homogeneously stable over a prolonged
period without any phase separation and/or precipitates.
Miscibility with other fuel additives is improved and the tendency
to form emulsions with water is suppressed. The high level of
intake valve and combustion chamber cleanliness achieved by the
modern fuel additives is not being worsened by the presence of the
complex ester mentioned in the fuel. Power loss in internal
com-bustion engines is minimized and acceleration of internal
combustion engines is im-proved. The presence of the complex ester
mentioned in the fuel also provides for an improved lubricating
performance of the lubricating oils in the internal combustion
engine.
[0120] The examples which follow are intended to further illustrate
the present invention without restricting it.
EXAMPLES
[0121] All complex esters of the following examples were prepared
according to the teachings of WO 99/16849, more precisely according
to the general procedure as follows:
[0122] The ratio of all three components, i.e. of mono fatty acids,
of dicarboxylic acids or dimeric acids, respectively (together
"diacids"), and of triols, was choosen in a way that OH and COOH
groups were present in equimolar amounts. All reactants were added
to the reactor and heated to approximately 140.degree. C. Then, the
temperature was stepwise increased to a maximum temperature of
approximately 250.degree. C. until the acid number was below 5 mg
KOH/g. In case a tin catalyst was necessary to reach this level of
residual acid number, the catalyst was removed by filtration.
[0123] The following table shows the composition of the complex
esters prepared (Examples 1a, 1b and 1c are for comparison,
Examples 2 and 3 are according to the present invention):
TABLE-US-00001 mono fatty acid "diacid" Triol Example 1a oleic acid
dimeric tallow fatty acid trimethylol- (comparison) (18 wt. % in
the complex propane ester) Example 1b oleic acid dimeric tallow
fatty acid trimethylol- (comparison) (6 wt. % in the complex
propane ester) Example 1c oleic acid dimeric tallow fatty acid
trimethylol- (comparison) (39 wt. % in the complex propane ester)
Example 2 isostearic sebacic acid pentaerythrol (invention) acid
(15 wt. % in the complex ester) Example 3 C.sub.8-C.sub.10 adipinic
acid trimethylol- (invention) acid (13 wt. % in the complex propane
ester)
Example 4
Preparation of Gasoline Performance Package "GPP 1"
[0124] 150 mg/kg of the complex ester of Example 1a, 1b, 1 c, 2 or
3 above were mixed with a customary gasoline performance package
containing as detergent additive component Kerocom.RTM. PIBA (a
polyisobutene monoamine made by BASF SE, based on a poly-isobutene
with M.sub.n=1000) and usual polyether-based carrier oils, Solvent
Naphtha as a diluent and corrosion inhibitors in customary
amounts.
Example 5
Engine Cleanliness Tests with GPP 1
[0125] In order to demonstrate that the complex esters according to
the present invention of Examples 2 and 3 do not decrease engine
cleanliness and that the complex esters of the art of Example 1
exhibit worse performance, the average IVD values were deter-mined
with gasoline performance package of Example 4 (GPP 1) and, for
comparison, with the same gasoline performance package (GPP 1) with
the customary detergent additive component Kerocom.RTM. PIBA but
without any complex ester, each according to CEC F-20-98 with a
Mercedes Benz M111 E engine using a customary RON 95 E10 gasoline
fuel and a customary RL-223/5 engine oil. The following table shows
the results of the determinations:
TABLE-US-00002 Additive average IVD [mg/valve] GPP 1 without any
complex ester 12 GPP 1 with 150 mg/kg of Example 1a 29 GPP 1 with
150 mg/kg of Example 1b 21 GPP 1 with 150 mg/kg of Example 1c 166
GPP 1 with 150 mg/kg of Example 2 9 GPP 1 with 150 mg/kg of Example
3 6
Example 6
Fuel Economy Tests
[0126] A typical low sulphur US E10 gasoline was additized with the
gasoline performance package of Example 4 (GGP 1) containing 150
mg/kg the complex ester of Example 2 or 3, respectively, and used
to determine fuel economy in a fleet test with three different
automobiles according to U.S. Environmental Protection Agency Test
Protocol, C.F.R. Title 40, Part 600, Subpart B. For each
automobile, the fuel consumption was determined first with
unadditized fuel and then with the same fuel which now, however,
comprised the above-specified gasoline performance package in the
dosage as specified above. The following fuel savings were
achieved:
TABLE-US-00003 2004 Mazda 3, 2.0 L l4: 1.03% (with Example 2);
0.75% (with Example 3) 2012 Honda Civic, 1.8 L l4. 1.02% (with
Example 2); 1.32% (with Example 3) 2010 Chevy HHR, 2.2 L l4: 1.53%
(with Example 2); 1.55% (with Example 3)
[0127] On average, over all automobiles used, the result was an
average fuel saving of 1.19% (with Example 2) and 1.21% (with
Example 3).
Example 7
Preparation of Gasoline Performance Package "GPP 2"
[0128] 150 mg/kg of the complex ester of Example 2 or 3,
respectively, above were mixed with a customary gasoline
performance package containing as detergent additive compo-nent
Kerocom.RTM. PIBA (a polyisobutene monoamine made by BASF SE, based
on a poly-isobutene with M.sub.n=1000) and usual polyether-based
carrier oils, kerosene as a diluent, demulsifiers and corrosion
inhibitors in customary amounts.
Example 8
Storage Stability
[0129] 48.0% by weight of GPP 2 above containing complex ester of
Example 2 or 3, respectively, and 37.7% by weight of xylene were
mixed at 20.degree. C. and stored thereafter in a sealed glass
bottle at -20.degree. C. for 42 days. At the beginning of this
storage period and then after each 7 days, the mixture was
evaluated visually and checked for possible phase separation and
precipitation. It is the aim that the mixture remains clear ("c"),
homogeneous ("h") and liquid ("l") after storage and does not
exhibit any phase separation ("ps") or precipitation ("pr"). The
following table shows the results of the evaluations:
TABLE-US-00004 after 7 days c, h, l (for Example 2) c, h, l (for
Example 3) after 14 days c, h, l (for Example 2) c, h, l (for
Example 3) after 21 days c, h, l (for Example 2) c, h, l (for
Example 3) after 28 days c, h, l (for Example 2) c, h, l (for
Example 3) after 35 days c, h, l (for Example 2) c, h, l (for
Example 3) after 42 days c, h, l (for Example 2) c, h, l (for
Example 3) Result: pass (for Example 2) pass (for Example 3)
* * * * *