U.S. patent application number 13/708374 was filed with the patent office on 2013-04-18 for fuel additives with improved miscibility and reduced tendency to form emulsions.
The applicant listed for this patent is Alfred Karl Jung, Markus Kummeter, Andrea Misske, Gero Nordmann, Dietmar Posselt, Ludwig VOELKEL. Invention is credited to Alfred Karl Jung, Markus Kummeter, Andrea Misske, Gero Nordmann, Dietmar Posselt, Ludwig VOELKEL.
Application Number | 20130091762 13/708374 |
Document ID | / |
Family ID | 40229834 |
Filed Date | 2013-04-18 |
United States Patent
Application |
20130091762 |
Kind Code |
A1 |
VOELKEL; Ludwig ; et
al. |
April 18, 2013 |
FUEL ADDITIVES WITH IMPROVED MISCIBILITY AND REDUCED TENDENCY TO
FORM EMULSIONS
Abstract
This invention relates to an additive package containing an
organic solvent, a detergent additive and a reaction product
mixture obtained by reacting a carboxylic acid compound of formula
(I): R.sup.1COOR.sup.2 with an alkanol amine of formula (II):
NHR.sup.3R.sup.4 to form a reaction product containing a
polysubstituted alkanol amine derivative, where the reaction is
performed by: (a) heating the carboxylic acid of formula (I) to a
first temperature; (b) adding thereto the alkanol amine of formula
(II) under controlled conditions avoiding an increase of
temperature above the first temperature range; (c) maintaining
temperature in the first temperature range; and (d) increasing the
temperature of the reaction mixture to a second temperature in a
second temperature range of 160 to 210.degree. C. and allowing
further reaction of residual free carboxylic acid molecules with
any reactive group in the reaction mixture.
Inventors: |
VOELKEL; Ludwig;
(Limburgerhof, DE) ; Posselt; Dietmar;
(Heidelberg, DE) ; Jung; Alfred Karl; (Rockwood,
MI) ; Kummeter; Markus; (Heddesheim, DE) ;
Nordmann; Gero; (Charlotte, NC) ; Misske; Andrea;
(Speyer, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
VOELKEL; Ludwig
Posselt; Dietmar
Jung; Alfred Karl
Kummeter; Markus
Nordmann; Gero
Misske; Andrea |
Limburgerhof
Heidelberg
Rockwood
Heddesheim
Charlotte
Speyer |
MI
NC |
DE
DE
US
DE
US
DE |
|
|
Family ID: |
40229834 |
Appl. No.: |
13/708374 |
Filed: |
December 7, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12681788 |
Apr 6, 2010 |
|
|
|
PCT/EP08/64021 |
Oct 17, 2008 |
|
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13708374 |
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Current U.S.
Class: |
44/386 |
Current CPC
Class: |
C07C 233/20 20130101;
C10L 1/22 20130101; C10L 1/143 20130101; C10L 1/2387 20130101; C10L
1/238 20130101; C10L 1/1608 20130101; C10L 1/1824 20130101; C10L
1/1985 20130101; C10L 1/224 20130101; C10L 1/2383 20130101; C10L
1/221 20130101 |
Class at
Publication: |
44/386 |
International
Class: |
C10L 1/22 20060101
C10L001/22 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 19, 2007 |
EP |
07118841.1 |
Claims
1. An additive package, comprising: an organic solvent; a detergent
additive; and a reaction product mixture, obtained by reacting a
carboxylic acid compound of formula (I) with an alkanol amine of
formula (II) to form a reaction product comprising a
poly-substituted alkanol amine derivative: R.sup.1COOR.sup.2 (I);
NHR.sup.3R.sup.4 (II), wherein: R.sup.1 is an aliphatic
C.sub.1-C.sub.30-hydrocarbon radical; R.sup.2 is hydrogen or alkyl,
mono- or polyhydroxyalkyl, or ammonium; R.sup.3 and R.sup.4
independently of each other represent hydrogen or a residue of
formula (III): --[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.zR.sup.5
(III); R.sup.3 and R.sup.4 are not both hydrogen atoms; x and z are
independently from each other integers from 1 to 6; y is 0 or an
integer of 1 to 3; R.sup.5 is hydroxyl or a residue of formula
(IV): --NH(CH.sub.2).sub.z'OH (IV); z' is an integer from 1 to 6;
and the reaction is performed by: (a) heating the carboxylic acid
of formula (I) to a first temperature in a first temperature range
of 100 to 155.degree. C.; (b) adding thereto the alkanol amine of
formula (II) under controlled conditions avoiding an increase of
temperature above the first temperature range; (c) maintaining
temperature in the first temperature range; and (d) increasing the
temperature of the reaction mixture to a second temperature in a
second temperature range of 160 to 210.degree. C. and allowing
further reaction of residual free carboxylic acid molecules with
any reactive group in the reaction mixture, such that a molar ratio
of carboxyl groups of the carboxylic acid of formula (I) to a molar
sum of OH and NH groups of the alkanol amine of formula (II) is in
a range of about 1.8:3 to 3:3.
2. The additive package of claim 1, comprising said polysubstituted
alkanol amine derivative in a proportion of more than 20 wt. %,
based on a total weight of the product.
3. The additive package of claim 1, wherein the molar ratio of
carboxyl groups of the carboxylic acid of formula (I) to the molar
sum of OH and NH groups of the alkanol amine of formula (II) is in
a range of about 1.9:3 to 2.5:3.
4. The additive package of claim 1, wherein the first temperature
during at least one of (b), (c) and (d) is maintained in a range of
120 to 135.degree. C.
5. The additive package of claim 1, wherein the second temperature
in (d) is maintained in a range of 175 to 190.degree. C.
6. The additive package of claim 1, wherein: x and z are
independently from each other integers from 1, 2 or 3; y is 0 or 1;
and z' is an integer of 1, 2, or 3.
7. The additive package of claim 1, wherein the compound of formula
(I) is at least one selected from the group consisting of a
C.sub.8-C.sub.30-carboxylic acid and an alkyl ester thereof.
8. The additive package of claim 1, wherein the compound of formula
(II) is a polyaminoalkanol, wherein: one of R.sup.3 and R.sup.4 is
hydrogen and the other is the residue of formula (III); x is 2 or
3; y is 0 or 1; z is 2 or 3; and R.sup.5 is hydroxyl or the residue
of formula (IV).
9. A method of improving a storage stability of an additive
package, the method comprising adding to said package at least one
reaction product mixture obtained by reacting a carboxylic acid
compound of formula (I) with an alkanol amine of formula (II) to
form a reaction product comprising a polysubstituted alkanol amine
derivative: R.sup.1COOR.sup.2 (I); NHR.sup.3R.sup.4 (II), wherein:
R.sup.1 is an aliphatic C.sub.1-C.sub.30-hydrocarbon radical;
R.sup.2 is hydrogen or alkyl, mono- or polyhydroxyalkyl, or
ammonium; R.sup.3 and R.sup.4 independently of each other represent
hydrogen or a residue of formula (III):
--[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.zR.sup.5 (III); R.sup.3
and R.sup.4 are not both hydrogen atoms; x and z are independently
from each other integers from 1 to 6; y is 0 or an integer of 1 to
3; R.sup.5 is hydroxyl or a residue of formula (IV):
--NH(CH.sub.2).sub.z'OH (IV); z' is an integer from 1 to 6; the
reaction is performed by: (a) heating the carboxylic acid of
formula (I) to a first temperature in a first temperature range of
100 to 155.degree. C.; (b) adding thereto the alkanol amine of
formula (II) under controlled conditions avoiding an increase of
temperature above the first temperature range; (c) maintaining
temperature in the first temperature range; and (d) increasing the
temperature of the reaction mixture to a second temperature in a
second temperature range of 160 to 210.degree. C. and allowing
further reaction of residual free carboxylic acid molecules with
any reactive group in the reaction mixture, such that a molar ratio
of carboxyl groups of the carboxylic acid of formula (I) to a molar
sum of OH and NH groups of the alkanol amine of formula (II) is in
a range of about 1.8:3 to 3:3; and the additive package comprises a
detergent additive in an organic solvent.
10. The method of claim 9, wherein the detergent additive is at
least one selected from the group consisting of a polyalkene
monoamine, a polyalkene Mannich amine and a polyalkene
succinimide.
11. A reaction product mixture, obtained by reacting a carboxylic
acid compound of formula (I) with an alkanol amine of formula (II)
to form a reaction product comprising a polysubstituted alkanol
amine derivative: R.sup.1COOR.sup.2 (I); NHR.sup.3R.sup.4 (II),
wherein: R.sup.1 is an aliphatic C.sub.1-C.sub.30-hydrocarbon
radical; R.sup.2 is hydrogen or alkyl, mono- or polyhydroxyalkyl,
or ammonium; R.sup.3 and R.sup.4 independently of each other
represent hydrogen or a residue of formula (III):
--[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.nR.sup.5 (III), such
that R.sup.3 and R.sup.4 are not both hydrogen atoms; x and z are
independently from each other integers from 1 to 6; y is 0 or an
integer of 1 to 3; R.sup.5 is hydroxyl or a residue of formula
(IV): --NH(CH.sub.2).sub.z'OH (IV); z' is an integer from 1 to 6;
and the reaction is performed by: (a) heating the carboxylic acid
of formula (I) to a first temperature in a first temperature range
of 100 to 155.degree. C.; (b) adding thereto the alkanol amine of
formula (II) under controlled conditions avoiding an increase of
temperature above the first temperature range; (c) maintaining
temperature in the first temperature range; and (d) increasing the
temperature of the reaction mixture to a second temperature in a
second temperature range of 160 to 210.degree. C. and allowing
further reaction of residual free carboxylic acid molecules with
any reactive group in the reaction mixture, such that a molar ratio
of carboxyl groups of the carboxylic acid of formula (I) to a molar
sum of OH and NH groups of the alkanol amine of formula (II) is in
a range of about 1.8:3 to 3:3.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. patent
application Ser. No. 12/681,788 filed Apr. 6, 2010, which is a
National Stage of PCT/EP08/64021 filed Oct. 17, 2008 and claims the
benefit of priority from EP patent application no. 07118841.1 filed
Oct. 19, 2007.
FIELD OF THE INVENTION
[0002] The present invention relates to novel fuel additives
obtainable by reacting carboxylic acids and alkanol amines under
specific conditions. Said additives show an improved performance in
fuels, like gasoline. The invention also relates to methods of
preparing the same; additive packages containing said additives;
and methods of improving the storage stability of additive packages
comprising a detergent additive in an organic solvent.
BACKGROUND OF THE INVENTION
[0003] Reaction products of fatty acid derivatives and alkanol
mono- or polyamines are known to be useful additives for
application in gasoline and diesel.
[0004] Chapter 7: Organic Friction Modifiers, Lubricant Additives:
Chemistry and Applications; Leslie R. Rudnick, CRC 2003, ISBN
0824708571. Kenbeek and Buenemann explain that non-acetic organic
friction modifiers are preferably long straight-chain molecules
with small polar heads. They are described to form adsorption
layers on the surface where multiple molecules are adsorbed by
hydrogen bonding and Debye orientation forces. Van der Waals forces
cause the molecules to align themselves such that they form
multimolecular clusters that are parallel to each other. Examples
of organic friction modifiers are oleylamide and glycerol
mono-oleate (GMO).
[0005] EP 1 295 933 describes deposit control additives for direct
injected engines available by reaction of monocarboxylic acids and
polyamines. Most preferred is a molar ratio of 1 to 1.5 moles of
monocarboxylic acid and 1 mole of polyamine. Specific preferred
examples are the reaction products of equimolar amounts of tallow
fatty acid or oleic acid and AEAE. According to the general
procedure disclosed therein the reaction is performed at reflux
temperature which is in the range of 150 to 175.degree. C. There is
no suggestion made in said document with respect to choosing the
reaction conditions (molar ratio and/or reaction temperature) such
that polysubstituted alkanolamines are preferentially formed. In
particular, it is not suggested to control the kinetics of the
reaction by selecting a suitable temperature profile.
[0006] EP 1 435 386 describes fatty acid alkanol amides, which
improve the acceleration properties of internal combustion engines.
This document describes alkanol monoamides obtainable by reaction
of 1 mole of fatty acid or it's esters and 1 mole of an alkanol
monoamine.
[0007] EP1 272 594 describes the use of friction modifiers, which
are the reaction products of certain natural or synthetic
carboxylic acid glyceryl esters and alkanol amines in combination
with a detergent additive in gasoline for improving the delivery of
the friction modifier to the lubricant of the engine. The reaction
of preparing the friction modifier is performed without applying a
specific temperature profile. The specific selection of a
significant molar excess of the alkanol amine is neither suggested
nor exemplified. Similar friction modifiers are disclosed on WO
2007/053787 where it is suggested to use the same in combination
with a solvent, an alcohol and certain compatibilizer to form fuel
additive concentrates remaining fluid at -8.degree. C. or
below.
[0008] Even if these additives provide good performance, they have
significant disadvantages due to their polar structure.
[0009] Most of such components stabilize emulsions of hydrocarbon
fuel and water. Such emulsions can cause severe damage in modern
cars; additive suppliers therefore need to compensate this effect
by adding so called dehazers.
[0010] Furthermore most of such 1:1 adducts of a carboxylic acid
moiety and an alkanol amine show a strong tendency to form
multi-molecular clusters, which results in incompatibility with
typical detergent additives such as PIB monoamines, PIB Mannich
amines or PIB succinimides. Blends of such fatty acid amides with
PIB-based products therefore require expensive solvents such as
hydrophobic alcohols or comparable solubilizer.
[0011] Even if there are technical solutions to overcome these
problems, they will at least unfavourably increase costs so that
some of these additives are not economically advantageous.
[0012] The problem to be solved by the present invention,
therefore, was to develop additives, which show better solubility
and compatibility as well as milder emulsion behaviour than
conventional reaction products of fatty acids and alkanol amines,
while, preferably, maintaining a similar additive performance
profile. In particular, the additives of the present invention
should improve the storage stability of additive packages, in
particular at temperatures below 0.degree. C., and should improve
the phase separation of fuel/water emulsions so that less or no
dehazer is required for preparing the fuel.
SUMMARY OF THE INVENTION
[0013] Surprisingly is was found that the conversion products of
carboxylic acids and alkanol amines obtained under specific
reaction conditions and which result in the formation of specific
complex reaction mixtures comprising substantial proportions of low
polarity constituents still have sufficient additive performance in
the fuel, in particular gasoline. An addition, due to their lower
polarity they are better compatible with other additive compounds
and need no or less dehazer to compensate emulsion effects.
DETAILED DESCRIPTION OF THE INVENTION
A) Preferred Embodiments
[0014] A first embodiment of the invention relates to a reaction
product, obtainable by reacting, preferably in a thermal
condensation reaction, a carboxylic acid (or carboxylate) compound
of formula I
R.sup.1COOR.sup.2 (I)
in which R.sup.1 is an aliphatic C.sub.1-C.sub.30-hydrocarbon
radical; R.sup.2 is hydrogen or alkyl, mono- or polyhydroxyalkyl,
or ammonium, with an alkanol amine of the formula II
NHR.sup.3R.sup.4 (II)
wherein R.sup.3 and R.sup.4 are independently selected from
hydrogen atoms and linear or branched-chain hydrocarbon groups, the
carbon chain of which optionally being interrupted by one or more
--NH-- groups, and which optionally has at least one hydroxyl group
attached to a carbon atom, with the proviso that R.sup.3 and
R.sup.4 are not both hydrogen atoms and that at least one of said
residues R.sup.3 and R.sup.4 carries at least one hydroxyalkyl
group, in a molar ratio of the carboxyl groups (--COO--) of the
carboxylic acid of formula I to the molar sum of OH and NH groups
of the alkanol amine of formula II in a range and under reaction
conditions supporting the formation of a reaction product
comprising polysubstituted alkanol amine derivatives.
[0015] Preferably, said polysubstituted (as for example
polycarbonylated) alkanol amine derivatives are comprised in said
reaction product in a proportion of more than 20 wt.-%, preferably
more than 40 wt.-%, and in particular more than 60 wt.-%, based on
the total weight of the reaction product.
[0016] On the other hand 1:1 adducts are present in a total amount
of 20 wt.-% or less, more preferred at 15 wt.-% or less and most
preferred at a level of 10 wt.-% or less, like about 0.1 to about
10 or about 1 to about 8 or about 1.5 to about 5, about 2 to about
4 wt.-%, based on the total weight of the reaction product.
[0017] According to a further preferred embodiment the reaction
product of the invention is obtained by a process, wherein the
molar ratio of the carboxyl groups of the carboxylic acid of
formula I to the molar sum of OH and NH groups of the alkanol amine
of formula II is in the range of about 1.8:3 to 3:3, in particular
1.9:3 to 2.5:3.
[0018] Preferably said reaction is performed by [0019] a) heating
the carboxylic acid compound(s) of formula I (in substance or
dissolved/or dispersed in a suitable liquid which does not disturb
the reaction) to a first temperature in a first temperature range,
allowing the preferential reaction of the acid with amine group(s)
of the alkanol amine; [0020] b) adding thereto the alkanol amine
compound(s) of formula II (in substance or dissolved or dispersed
in a suitable liquid which does not disturb the reaction) under
controlled conditions in order to avoid an increase of the
temperature above said first temperature range; [0021] c) reacting
the compounds by maintaining the temperature in said first range;
[0022] d) and increasing the first temperature of the reaction
mixture to a second temperature in a second temperature range
allowing further condensation of residual free carboxylic acid
molecules with any reactive group in the reaction mixture,
preferably until the amount of water condensate is at least equal
to the theoretical amount of reaction water.
[0023] Preferably, the first temperature in step a), b) and/or c)
is kept in the range of about 100 to about 155.degree. C., as for
example about 110 to about 140.degree. C., or about 120 to about
135.degree. C.
[0024] Preferably, the second temperature in step d) is kept in the
range of 160 to 210.degree. C., as for example about 170 to about
200.degree. C., or about 175 to about 190.degree. C.
[0025] In a particularly preferred embodiment the reaction product
the additive is obtained by reacting a carboxylic acid compound
with an alkanol amine of formula II, wherein R.sup.3 and R.sup.4
independently of each other represent hydrogen or a residue of the
formula III
--[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.zR.sup.5 (III) [0026]
wherein [0027] x and z are independently from each other integers
from 1 to 6, preferably 1, 2, or 3, [0028] y is 0 or an integer of
1 to 3, preferably 0 or 1, and [0029] R.sup.5 is hydroxyl or a
residue of the formula IV
[0029] --NH(CH.sub.2).sub.zOH (IV) [0030] wherein z is as defined
above; with the proviso that R.sup.3 and R.sup.4 are not both
hydrogen atoms.
[0031] In a further particularly preferred embodiment the reaction
product is obtained from a compound of formula I, which is selected
from C.sub.2-C.sub.31- or C.sub.8-C.sub.31- or C.sub.8-C.sub.30- or
C.sub.10-C.sub.22-carboxylic acids and alkyl esters thereof.
[0032] Preferably the compound of formula II is selected from
polyamino alkanols, wherein one of the residues R.sup.3 and R.sup.4
is hydrogen and the other is a residue of the formula III, wherein
x is 2 or 3, y is 0 or 1, z is 2 or 3 and R.sup.5 is hydroxyl or a
residue of the formula IV.
[0033] According to another embodiment of the invention additive
packages are provided, comprising in a suitable organic solvent at
least one detergent additive and at least one reaction product as
defined above.
[0034] According to another embodiment of the invention a method of
improving the storage stability of additive packages wherein the
additive package comprises at least one detergent additive in an
organic solvent, which method comprises adding to said package at
least one reaction product of the invention. In particular, said
detergent additive is selected from as polyalkene monoamines,
polyalkene Mannich amines or polyalkene succinimides.
B) General Definitions
[0035] A "reaction product" as used herein means the product of a
specific reaction of at least one carboxylic acid compound or a
carboxylic acid compound containing first reactant, and at least
one alkanol amine or an alkanol amine containing second reactant as
explained in more detail below. The reaction product is complex in
nature, i.e. consists of a complex mixture of constituents, the
profile of which being substantially predetermined by the reaction
conditions of said conversion. The reaction product is, as such, a
suitable additive for fuels and normally need not be further
purified prior to use. The product may, however, be concentrated
(if necessary) in order to remove residual solvent or low molecular
constituents, like water or non-reacted reactants, if any.
[0036] The term "carboxylate compound" refers to any compound of
formula I as defined d above.
[0037] The term "aliphatic C.sub.1-C.sub.30-hydrocarbon radical"
denotes an acyclic radical which is composed substantially of
carbon atoms and hydrogen atoms and comprises from 1 to 30, as for
example 8 to 30 carbon atoms. The hydrocarbon radical is preferably
an alkyl, alkenyl, alkadienyl, alkatrienyl or polyenyl radical.
Those skilled in the art will appreciate the minimum numbers of
carbon atoms that need to be present in hydrocarbon radicals of
various degree of unsaturation.
[0038] An alkyl radical comprises C.sub.1-C.sub.8-alkyl radicals
which are linear or branched radicals having from 1 to 8 carbon
atoms. Examples thereof are the C.sub.1-C.sub.4-alkyl radicals
methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or
tert-butyl, and additionally pentyl, methylbutyl, 2-methylbutyl,
3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 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, trimethylpropyl, 1-ethyl-1-methylpropyl,
1-ethyl-2-methylpropyl, heptyl, octyl and their constitutional
isomers such as 2-ethylhexyl; or C.sub.8-C.sub.30-alkyl radicals
which are linear or branched radicals having from 8 to 30 carbon
atoms. Examples thereof are octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl,
pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl,
their constitutional isomers, higher homologs and constitutional
isomers thereof.
[0039] Alkenyl comprises C.sub.2-C.sub.8-alkenyl radicals which are
monounsaturated linear or branched hydrocarbon radicals having from
2 to 8 carbon atoms, as for example ethenyl, 1- or 2-propenyl, 1-,
2- and 3-butenyl, 2-methylpropen-3-yl, 2-methylpropen-1-yl, 1-, 2-,
3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1-, 2-, 3-, 4-, 5-
and 6-heptenyl 1-, 2-, 3-, 4-, 5-, 6- and 7-octenyl and also their
constitutional isomers; C.sub.8-C.sub.30-Alkenyl is a
monounsaturated linear or branched hydrocarbon radical having from
8 to 30 carbon atoms. Examples thereof are octenyl, nonenyl,
decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,
eicosenyl, hencosenyl, docosenyl, tricosenyl, tetracosenyl,
pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,
squalenyl, their constitutional isomers, higher homologs and
constitutional isomers thereof.
[0040] Alkandienyl radicals comprise C.sub.4-C.sub.8-alkadienyl
radicals which are diunsaturated linear or branched hydrocarbon
radical having from 4 to 8 carbon atoms, as for example butadienyl,
pentadienyl, hexadienyl, heptadienyl or octadienyl and their
constitutional isomers; or C.sub.8-C.sub.30-alkadienyl radicals
which are diunsaturated linear or branched hydrocarbon radicals
having from 8 to 30 carbon atoms. Examples thereof are octadienyl,
nonadienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl,
tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl,
octadecadienyl, nonadecadienyl, eicosadienyl, hencosadienyl,
docosadienyl, tricosadienyl, tetracosadienyl, pentacosadienyl,
hexacosadienyl, heptacosadienyl, octacosadienyl, nonacosadienyl,
squaladienyl, their constitutional isomers, higher homologs and
constitutional isomers thereof. The olefinic double bonds may be
present in conjugated or isolated form
[0041] Alkantrienyl radicals comprise C.sub.6-C.sub.8-alkatrienyl
radicals which are tri-unsaturated linear or branched hydrocarbon
radical having from 6 to 8 carbon atoms, as for example
hexatrienyl, heptatrienly or octatrienyl; or
C.sub.8-C.sub.30-alkatrienyl radicals, which are triunsaturated
linear or branched hydrocarbon radicals having from 8 to 30 carbon
atoms. Examples thereof are octatrienyl, nonatrienyl, decatrienyl,
undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl,
pentadecatrienyl, hexadecatrienyl, heptadecatrienyl,
octadecatrienyl, nonadecatrienyl, eicosatrienyl, hencosatrienyl,
docosatrienyl, tricosatrienyl, tetracosatrienyl, pentacosatrienyl,
hexacosatrienyl, heptacosatrienyl, octacosatrienyl,
nonacosatrienyl, squalatrienyl, their constitutional isomers,
higher homologs and constitutional isomers thereof. The olefinic
double bonds may be present in conjugated or isolated form.
[0042] Polyenyl radicals are in particular
C.sub.8-C.sub.30-polyenyl radicals which are generally unsaturated
linear or branched aliphatic hydrocarbon radicals having from 8 to
30 carbon atoms and four, five, six or more olefinic nonvicinal
double bonds Examples thereof are the higher unsaturated analogs of
the above C.sub.8-C.sub.30-alkadi- and trienyl residues.
[0043] Unless otherwise stated the term "alkyl", as for example in
the context of residue R.sup.2 refers to C.sub.1-C.sub.8-alkyl as
defined above.
[0044] The term "mono- or polyhydroxyalkyl" refers to
C.sub.1-C.sub.8-hydroxyalkyl which is a linear or branched alkyl
radical having from 1 to 8, in particular from 1 to 4 carbon atoms,
in which at least one hydrogen atom, for example 1, 2, 3, or 4 of
the hydrogen atoms, is/are replaced by a hydroxyl group. Examples
thereof are, hydroxymethyl, 2-hydroxy-1-ethyl, 2- and
3-hydroxy-1-propyl, 2-, 3- and 4-hydroxy-1-butyl, 2-, 3-, 4- and
5-hydroxy-1-pentyl, 2-, 3-, 4-, 5- and 6-hydroxy-1-hexyl, 2-, 3-,
4-, 5-, 6- and 7-hydroxy-1-heptyl, 2-, 3-, 4-, 5-, 6-, 7- and
8-hydroxy-1-octyl, 2,3-dihydroxy-1-propyl and their constitutional
isomers. If R.sup.2 represents a polyhydroxyalkyl residue, said
hydroxy groups are, preferably, not further esterified. In
particular, compounds of formular I do not comprise polyol
polyester, as for example triglycerides.
[0045] The term "hydroxyalkyl" refers to
C.sub.1-C.sub.8-hydroxyalkyl which is a linear or branched alkyl
radical having from 1 to 8, in particular from 1 to 4 carbon atoms,
in which one hydrogen atom is replaced by a hydroxyl group.
Suitable examples are stated above.
[0046] A "linear or branched-chain hydrocarbon group, the carbon
chain of which optionally being interrupted by one or more --NH--
groups optionally carrying at least one hydroxyalkyl group",
comprises a terminal hydroxyalkyl group which is a mono- or
polyhydroxyalkyl group as defined above, and comprises optionally
at least one C.sub.1-C.sub.6-alkylene group, optionally substituted
by 1 or more, like 1, 2, or 3 hydroxyl groups, whereby two or more
of said alkylene groups being linked together by a --NH-group.
[0047] "C.sub.1-C.sub.6-Alkylene" is a linear or branched bridging
hydrocarbon group having 2, 3, 4, 5 or 6 carbon atoms, such as
1,2-ethylene, 1,2- and 1,3-propylene, 1,2-, 1,3-, 2,3- and
1,4-butylene, 2,2-dimethyl-1,2-ethylene, 1,1-dimethyl-1,2-ethylene,
1,5-pentylene, 1,6-hexylene and constitutional isomers thereof.
[0048] A "polysubstituted" or "polycarbonylated" alkanol amine
derivative is derived from an polyfunctional alkanol amine, as for
example an alkanol polyamine, wherein more than one functional
groups (--NH-- or --OH groups) of which, being substituted by a
carbonyl residue of the formula --CO(hycrocarbyl), wherein
hydrocarbyl has the same meanings as an "aliphatic
C.sub.1-C.sub.30-hydrocarbon radical" as already defined above. In
particular said substituents may be derived from same or different
C.sub.10-C.sub.22-carboxylic acids. The term "polysubstituted"
encompasses di-, tri-, tetra and higher substituted alkanol amine
derivatives.
[0049] A "C.sub.2-C.sub.31-carboxylic acid" represents a
straight-chain or branched, saturated or mono- or poly-unsaturated
C.sub.1-30-hydrocarbyl residue. In particular, said residue is a
straight-chain mono- or poly-unsaturated hydrocarbyl residue or a
mixture of such residues with an average length of 1-30, 1-29,
preferably 5-25 carbon atoms. Particularly preferred residues are:
[0050] residues derived from saturated, straight-chain carboxylic
acids: CH.sub.3--, C.sub.2H.sub.5--; C.sub.3H.sub.7--;
C.sub.4H.sub.9--; C.sub.5H.sub.11--; C.sub.6H.sub.13--;
C.sub.7H.sub.15--, C.sub.8H.sub.17--; C.sub.9H.sub.19--;
C.sub.10H.sub.21--; C.sub.11H.sub.23--; C.sub.12H.sub.25--;
C.sub.13H.sub.27--; C.sub.14H.sub.29--; C.sub.15H.sub.31--;
C.sub.16H.sub.33--; C.sub.17H.sub.35--; C.sub.18H.sub.37--;
C.sub.19H.sub.39--; C.sub.20H.sub.41--; C.sub.21H.sub.43--;
C.sub.23H.sub.47--; C.sub.24H.sub.49; --C.sub.25H.sub.51--;
C.sub.29H.sub.59--; C.sub.30H.sub.61; [0051] residues derived from
saturated, branched carboxylic acids: iso-C.sub.3H.sub.7--;
iso-C.sub.4H.sub.9--; iso-C.sub.18H.sub.37--; [0052] residues
derived from mono-unsaturated, straight-chain carboxylic acids:
C.sub.2H.sub.3--; C.sub.3H.sub.5--; C.sub.15H.sub.29--;
C.sub.17H.sub.33--; C.sub.21H.sub.41--; [0053] residues derived
from two-fold unsaturated, straight-chain carboxylic acids:
C.sub.5H.sub.7--; C.sub.17H.sub.31--; [0054] residues derived from
three-fold unsaturated, straight-chain carboxylic acids:
C.sub.17H.sub.29--; [0055] residues derived from four-fold
unsaturated, straight-chain carboxylic acids: C.sub.19H.sub.31--;
[0056] residues derived from five-fold unsaturated, straight-chain
carboxylic acids: C.sub.21H.sub.33--.
[0057] Said hydrocarbyl residue may also be derived from fatty acid
mixtures as obtained from naturally occurring oils and fats.
Non-limiting examples thereof are olive oil, palm oil, palm cernel
oil, peanut oil, rapeseed oil, safflower oil, sesame oil, sunflower
oil, soy bean oil, to beef tallow oil, lard oil, castor oil,
cottonseed oil, corn oil, soybean oil, whale oil, and coconut oil.
As examples of suitable fatty acids there may be mentioned
monocarboxylic acids such as capric, lauric, myristic, palmitic,
stearic, behenic, oleic, petroselinic, elaidic, palmitoleic,
linoleic, linolenic and erucic acid.
[0058] The term "alkanol amines" has to be understood broadly. It
comprises monoalkanolamines, dialkanolamines, and so forth. The
alkanolamine can possess one or more additional O and/or N
functionalities in addition to the one amino group. and at least
one hydroxy group. Suitable alkanolamines include monoethanolamine,
diethanolamine, propanolamine, isopropanolamine, dipropanolamine,
di-isopropanolamine, butanolamines, and polyaminoalkanols like
aminoethylaminoethanols, e.g., 2-(2-aminoethylamino)ethanol
(AEAE)
[0059] Alkanol amines are, for example, compounds of formula II
wherein at least one of the residues R.sup.3 and R.sup.4 represents
--[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.zR.sup.5 wherein R.sup.5
is hydroxyl or NH(CH.sub.2).sub.zOH. Suitable examples of groups of
the formula --[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.z-- are
C.sub.2H.sub.4--NH .sub.nC.sub.2H.sub.4, CH.sub.2).sub.3--NH
.sub.n(CH.sub.2).sub.3--, CH.sub.2--CH(CH.sub.3)--NH
.sub.nCH.sub.2--CH(CH.sub.3)--, CH(CH.sub.3)--CH.sub.2--NH
.sub.nCH(CH.sub.3)--CH.sub.2--, CH.sub.2).sub.4--NH
.sub.n(CH.sub.2).sub.4--, wherein n is 0, 1 or 2.
[0060] In one particular group one of R.sup.3 and R.sup.4
represents H, and in the other R.sup.5 is hydroxyl and
--[(CH.sub.2).sub.xNH].sub.y(CH.sub.2).sub.z is selected from
C.sub.2H.sub.4--NH .sub.nC.sub.2H.sub.4, CH.sub.2).sub.3--NH
.sub.n(CH.sub.2).sub.3--, CH.sub.2--CH(CH.sub.3)--NH
.sub.nCH.sub.2--CH(CH.sub.3)--, CH(CH.sub.3)--CH.sub.2--NH
.sub.nCH(CH.sub.3)--CH.sub.2--, CH.sub.2).sub.4--NH
.sub.n(CH.sub.2).sub.4--, while n is 1 or 2.
C) Examples of Reaction Products
[0061] In a non-limiting example of the present invention the
reaction product may represent a complex product mixture, which is
characterized by a high proportion of polysubstituted, i.e. at
least two-fold substituted, alkanol polyamines (or
polyaminoalkanols). In particular, the reaction mixture is
characterized by a high proportion of constituents, which are
selectively carbonylated at primary and/or secondary amino
groups.
[0062] Preferably, such reaction products are obtainable by
reaction of an alkanol amine selected from the above-identified
group of specific alkanol amines with a carboxylic acid containing
reagent under conditions defined herein.
[0063] Exemplified by AEAE as reactant of formula II the reaction
product formed (when a molar excess of a fatty acid is used) may
contain main constituents A, B and C (as depicted below), which
are: the main diamide product (A), optionally in admixture with the
corresponding (analytically difficult to distinguish)
monoamidoester, each of which carrying two carbonyl residues; the
fully substituted diamidoester (B) carrying three carbonyl groups;
and the monoamide (C). The reaction mixture may also contain minor
amounts of unreacted oleic acid (D) (1-5%) and AEAE (<0.1%) as
well as significant amounts (10-20%) of unidentified by-products
(it is presumed that i.a. pyrazidins, imidazolins and ethers are
produced). The kinetically controlled first step of the reaction,
performed at about 130.degree. C., favors the formation of the main
component, in particular the diamide (A), while the less specific
reaction conditions in the second reaction step at about
180.degree. C. result in the formation of the diamidoester (B).
##STR00001##
[0064] It is well understood by a skilled reader that the specific
conditions exemplified herein may be changed without changing the
general teaching of the present invention. For example, it is
possible to change the order of adding reactants to the reaction
mixture, to pre-heat the reactants, if necessary, to add one or
more solvents which may be removed after the end of the reaction.
In addition it may be possible to remove, if necessary the water as
formed during the course of the condensation reaction. Suitable
catalysts well-known in the art might also be used.
[0065] As suitable solvents there may be used any solvent, which
does not negatively affect the conversion reaction, and, optionally
which is compatible with the other constituents of an additive
package or the fuel to which the additive of the invention has to
be added, so that it is not necessary to remove the solvent prior
to use. As examples there may be mentioned toluene, xylene or any
other aromatic solvent; dioxane, dialkyl glycol and dialkyl oligo
glycols.
D) Further Additive Components
[0066] The reaction products of the present invention may be added
to the fuel as friction modifier, lubricity additive, detergent or
deposit control additive, acceleration improver, or corrosion
inhibitor
[0067] The reaction products of the invention may be added to the
fuels individually or in a mixture with further effective additive
components (co-additives) as exemplified in ore detail below.
D1) Detergent Additives
[0068] Examples include additives comprising detergent action
(hereinafter referred to as detergent additives). This detergent
additive has at least one hydrophobic hydrocarbon radical having a
number-average molecular weight (Mn) of from 85 to 20 000 and at
least one polar moiety selected from:
(a) mono- or polyamino groups having up to 6 nitrogen atoms, of
which at least one nitrogen atom has basic properties; (b) nitro
groups, if appropriate in combination with hydroxyl groups; (c)
hydroxyl groups in combination with mono- or polyamino groups, in
which at least one nitrogen atom has basic properties; (d) carboxyl
groups or their alkali metal or their alkaline earth metal salts;
(e) sulfonic acid groups or their alkali metal or alkaline earth
metal salts; (f) polyoxy-C.sub.2- to -C.sub.4-alkylene groups which
are terminated by hydroxyl groups, mono- or polyamino groups, in
which at least one nitrogen atom has basic properties, or by
carbamate groups; (g) carboxylic ester groups; (h) moieties derived
from succinic anhydride and having hydroxyl and/or amino and/or
amido and/or imido groups; and/or (i) moieties obtained by Mannich
reaction of substituted phenols with aldehydes and mono- or
polyamines.
[0069] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel, has a
number-average molecular weight (Mn) of from 85 to 20 000,
especially from 113 to 10 000, in particular from 300 to 5000.
Typical hydrophobic hydrocarbon radicals, especially in conjunction
with the polar moieties (a), (c), (h) and (i), include the
polypropenyl, polybutenyl and polyisobutenyl radical each having
Mn=from 300 to 5000, especially from 500 to 2500, in particular
from 700 to 2300.
[0070] Non-limiting examples of the above groups of detergent
additives include the following:
[0071] Additives comprising mono- or polyamino groups (a) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or conventional (i.e. having predominantly internal
double bonds) polybutene or polyisobutene having Mn=from 300 to
5000. When polybutene or polyisobutene having predominantly
internal double bonds (usually in the beta and gamma position) 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
polyamines, such as dimethylaminopropylamine, ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Corresponding additives based on polypropene are described in
particular in WO-A-94/24231.
[0072] Further preferred additives comprising monoamino groups (a)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P=from 5
to 100 with nitrogen oxides or mixtures of nitrogen oxides and
oxygen, as described in particular in WO-A-97/03946.
[0073] Further preferred additives comprising monoamino groups (a)
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.
[0074] Additives comprising nitro groups (b), if appropriate in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P=from
5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of
nitrogen oxides and oxygen, as described in particular in
WO-A-96/03367 and 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).
[0075] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (c) are in particular reaction products
of polyisobutene epoxides obtainable from polyisobutene having
preferably predominantly terminal double bonds and Mn=from 300 to
5000, with ammonia or mono- or polyamines, as described in
particular in EP-A-476 485.
[0076] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (d) are preferably copolymers of
C.sub.2-C.sub.40-olefins with maleic anhydride which have a total
molar mass of from 500 to 20 000 and of whose carboxyl groups some
or all 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.
[0077] Additives comprising sulfonic acid groups or their alkali
metal or alkaline earth metal salts (e) 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.
[0078] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (f) 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-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 polyether-amines, 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, isononylphenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0079] Additives comprising carboxylic ester groups (g) 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, from 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.
[0080] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups (h) are preferably corresponding derivatives of
polyisobutenyl-succinic anhydride which are obtainable by reacting
conventional or highly reactive polyisobutene having Mn=from 300 to
5000 with maleic anhydride by a thermal route or via the
chlorinated polyisobutene. Particular interest attaches to
derivatives with aliphatic polyamines such as ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Such gasoline fuel additives are described in particular in U.S.
Pat. No. 4,849,572.
[0081] Additives comprising moieties obtained by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines (i)
are preferably reaction products of polyisobutene-substituted
phenols with formaldehyde and mono- or polyamines such as
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine or dimethylaminopropylamine. The
polyisobutenyl-substituted phenols may stem from conventional or
highly reactive polyisobutene having Mn=from 300 to 5000. Such
"polyisobutene-Mannich bases" are described in particular in
EP-A-831 141.
[0082] For a more precise definition of the gasoline fuel additives
detailed individually, reference is explicitly made here to the
disclosures of the abovementioned prior art documents, incorporated
herewith by reference.
D2) Carrier Oils
[0083] The additive formulations according to the invention may
additionally be combined with still further customary components
and additives. Mention should be made here primarily of carrier
oils.
[0084] 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; and 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.
[0085] Examples of synthetic carrier oils which are useful in
accordance with the invention are selected from: polyolefins
(poly-alpha-olefins or poly(internal olefin)s), (poly)esters,
(poly)alkoxylates, polyethers, aliphatic polyether amines,
alkylphenol-started polyethers, alkylphenol-started polyether
amines and carboxylic esters of long-chain alkanols.
[0086] Examples of suitable polyolefins are olefin polymers having
Mn=from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or nonhydrogenated).
[0087] 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 polyether amines, 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.
[0088] 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.
[0089] 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, which are explicitly incorporated
herein by way of reference.
[0090] 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.18-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0091] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-10 102 913.6.
D3) Solvents and Co-Solvents
[0092] As examples of suitable solvent: any type of hydrocarbon
solvent may be mentioned, e.g. kerosene, heavy aromatic solvent
("solvent naphta heavy", "Solvesso 150"), xylene, paraffins,
petroleum, etc. Suitable co-solvents are for example t-BuOH,
i-BuOH, 2-ethyl hexanol, 2-propyl heptanol, butyl glycols,
D4) Dehazers
[0093] Dehazers/demulsifiers suitable for use in fuels are well
known in the art as. As non-limiting examples there may be
mentioned glycol oxyalkylate polyol blends (such as sold under the
trade designation TOLAD.TM. 9312), phenol/formaldehyde or
C.sub.1-18 alkylphenol/-formaldehyde resin oxyalkylates modified by
oxyalkylation with C.sub.1-18 epoxides and diepoxides (such as sold
under the trade designation TOLAD.TM. 9308), and C.sub.14 epoxide
copolymers cross-linked with diepoxides, diacids, diesters, diols,
diacrylates, dimethacrylates or diisocyanates, and blends thereof.
The glycol oxyalkylate polyol blends may be polyols oxyalkylated
with C.sub.14 epoxides. The C.sub.1-18 alkylphenol
phenol/-formaldehyde resin oxyalkylates modified by oxyalkylation
with C.sub.1-18 epoxides and diepoxides may be based on, for
example, cresol, t-butyl phenol, dodecyl phenol or dinonyl phenol,
or a mixture of phenol (such as a mixture of t-butyl phenol and
nonyl phenol). The dehazer should be used in an amount sufficient
to inhibit the hazing that might otherwise occur when the fuel
without the dehazer contacts water, and this amount will be
referred to herein as a "haze-inhibiting amount." Generally, this
amount is from about 0.1 to about 10 ppm based on the weight of the
fuel.
D5) Further Coadditives
[0094] Further customary additives (different from those of the
invention are) are corrosion inhibitors, for example based on
ammonium salts of organic carboxylic acids, said salts tending to
form films, or of heterocyclic aromatics for nonferrous metal
corrosion protection; antioxidants or stabilizers, for example
based on amines such as p-phenylenediamine, dicyclohexylamine or
derivatives thereof or of phenols such as 2,4-di-tert-butylphenol
or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; antistats;
metallocenes such as ferrocene; methylcyclopentadienylmanganese
tricarbonyl; lubricity additives, such as certain fatty acids,
alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines,
hydroxyacetamides or castor oil; and also dyes (markers). Amines
are also added, if appropriate, to lower the pH of the fuel.
Optionally anti valve seat recession additives may be used such as
sodium or potassium salts of polymeric organic acids.
E) Additive Packages
[0095] The additives may be added to the fuel individually or as a
concentrate (additive package) comprising a mixture of additives
and solvents as discussed above.
[0096] Usually reaction products of the invention are blended with
other fuel additives such as detergents, carrier oils, solvent,
co-solvent, and other optional minor components as described
above.
[0097] Typically, such packages may contain: [0098] reaction
product(s) of the invention: in proportions of about 5-80 or about
10-70 or about 10-40 wt.-%, based on the total weight of the
package; [0099] detergent(s): in proportions of about 10-80 or
about 20-70 or about 30-70 wt.-%, based on the total weight of the
package; [0100] carrier oil(s): in proportions of about 5-70 or
about 10-50 or about 10-40 wt.-%, based on the total weight of the
package; [0101] solvent(s): in proportions of about 5-70 or about
5-50 or about 10-50 wt.-%, based on the total weight of the
package; [0102] Co-solvent(s): in proportions of about 1-40 or
about 5-30 or about 5-20 wt.-%, based on the total weight of the
package; [0103] optionally: dehazer(s) (about <1%), corrosion
inhibitor(s) (about 0, 1-5%), conductivity improvers (about
<2%), each based on the total weight of the package; and
others.
[0104] All components are blended to an additive package, which
will be transported and stored for some days up to many months. In
particular in cold regions or regions with cold winter season the
package must therefore be stable for many weeks at deep
temperatures. Stable means that no phase separation or
precipitation occurs and the package must not become a solid
stuff.
[0105] For example, the fuel additive package of the present
invention remains a fluid at 0.degree. C., or -8.degree. C., or
-18.degree. C., or -20.degree. C., or -30.degree. C. or even
-40.degree. C. The fuel additive package in its fluid state is
substantially free of precipitate and/or sediment. The fluid may be
substantially free from suspended particles, flocculent, and
substantial phase separation (i.e., no multiple phases are
formed).
[0106] The reaction products of the invention are added to the fuel
typically in an amount of from 5 to 2,000 ppm by weight, in
particular from 10 to 1,500 or 10 to 500 ppm by weight. The other
components and additives mentioned above are, if desired, added in
amounts customary for the intended purpose.
E) Fuels
[0107] The additive compositions according to the invention are
useful in all conventional diesel and gasoline fuels, as described,
for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th
Ed. 1990, Volume A16, p. 719 ff.
[0108] For example, it is possible to use them in a gasoline fuel
having an aromatics content of not more than 60% by volume, for
example not more than 42% by volume or not more than 35% by volume,
and/or a sulfur content of not more than 2000 ppm by weight, for
example not more than 150 ppm by weight or not more than 10 ppm by
weight.
[0109] The aromatics content of the gasoline fuel is, for example,
from 10 to 50% by volume, for example from 30 to 42% by volume, in
particular from 32 to 40% by volume or not more than 35% by volume.
The sulfur content of the gasoline fuel is, for example, from 2 to
500 ppm by weight, for example from 5 to 100 ppm by weight, or not
more than 10 ppm by weight.
[0110] In addition, the gasoline fuel may have, for example, an
olefin content of up to 50% by volume, for example from 6 to 21% by
volume, in particular from 7 to 18% by volume; a benzene content of
up to 5% by volume, for example from 0.5 to 1.0% by volume, in
particular from 0.6 to 0.9% by volume, and/or an oxygen content of
up to 25% by volume, for example up to 10% by weight, or from 1.0
to 2.7% by weight, in particular from 1.2 to 2.0% by weight.
[0111] Examples of such gasoline fuels are in particular those
which simultaneously have an aromatics content of not more than 38
or 35% by volume, an olefin content of not more than 21% by volume,
a sulfur content of not more than 50 or 10 ppm by weight, a benzene
content of not more than 1.0% by volume and an oxygen content of
from 1.0 to 2.7% by weight.
[0112] The contents of alcohols and ethers in the gasoline fuel may
vary over a wide range. Examples of typical maximum contents are
15% by volume for methanol, 65% by volume for ethanol, 20% by
volume for isopropanol, 15% by volume for tert-butanol, 20% by
volume for isobutanol and 30% by volume for ethers having 5 or more
carbon atoms in the molecule.
[0113] The summer vapor pressure of the gasoline fuel is typically
not more than 70 kPa, in particular 60 kPa (each at 37.degree.
C.).
[0114] The RON of the gasoline fuel is generally from 75 to 105. A
typical range for the corresponding MON is from 65 to 95.
[0115] The specifications mentioned are determined by customary
methods (DIN EN 228).
[0116] The invention will now be illustrated in detail with
reference to the working examples, which follow:
Experimental Part
Example 1
Reaction Product of Coconut Oil Methyl Ester and Diethanol Amine
(Molar Ratio: 1:1)
[0117] A 5 L four-neck glass reactor equipped with condenser,
automatic injection equipment, internal temperature control and
anchor stirrer was charged with 2200 g of coconut methyl ester
(technical grade: ester content, % (m/m): 96. 5 min, kinematic
viscosity at 40.degree. C., mm.sup.2/s: 2.0-4.5) and heated to
150.degree. C. 1050 g of diethanol amine was added at this
temperature within 30 minutes. The reaction mixture was kept at
150.degree. C. for 4 hours, and than heated up for 1 hour to
160.degree. C. to completely remove residual methanol. The
resulting product was yellow oil.
Example 2
Reaction Product of Coconut Oil Methyl Ester and Diethanol Amine
(Molar Ratio: 2:1)
[0118] According to procedure of example 1 3000 g of coconut methyl
ester (technical grade: ester content, % (m/m): 96. 5 min,
kinematic viscosity at 40.degree. C., mm.sup.2/s: 2.0-4.5) and 716
g diethanol amine were reacted to a yellow oil.
Example 3
Reaction Product of Coconut Oil Methyl Ester and Diethanol Amine
(Molar ratio: 3:1)
[0119] According to procedure of example 1 3000 g of coconut methyl
ester (technical grade: ester content, % (m/m): 96.5 min, kinematic
viscosity at 40.degree. C., mm.sup.2/s: 2.0-4.5) and 477 g
diethanol amine were reacted to a yellow oil.
Example 4
Reaction Product of Oleic Acid and AEAE (Molar Ratio: 1:1)
[0120] A 250 ml glass flask equipped with a condenser was charged
with 56.4 g of oleic acid
[0121] (approx. 0.2 moles) and heated up to 130.degree. C. At this
temperature 20.8 g (0.2 moles) of amino ethyl ethanolamine were
added within 10 minutes. After stirring for three hours at this
temperature the reaction mixture was heated up to 180.degree. C.
and kept at this temperature for 5 hours. 66 g of brown oil was
yielded which solidified after few hours to a light brown wax.
Amine number was 124 mgKOH/g.
Example 5
Reaction Product of Oleic Acid and AEAE (Molar Ratio: 2:1)
[0122] Oleic acid and amino ethyl ethanolamine were reacted as
described in Example 4 but in a molar ratio of 2:1. Resulting
product was a light brown wax with an amine number of 14
mgKOH/g.
Example 6
Reaction Product of Oleic Acid and AEAE (Molar Ratio: 3:1)
[0123] Oleic acid and amino ethyl ethanolamine were reacted as
described in Example 4 but in a molar ratio of 3:1. Resulting
product was brown oil with an amine number of 6.2 mgKOH/g.
Test Example 1
[0124] To demonstrate the effect of different molar ratios, three
different products (prepared according to Example 4, 5 and 6) were
blended with polyisobutene amine (PIBA), polyoxyalkylene carrier
oil and different amounts of solvent to result in typical fuel
additive compositions.
[0125] The storage stability at low temperature and the tendency to
stabilize emulsions were examined. Standard test procedures were
applied. The results are summarized in the following Table 1.
TABLE-US-00001 TABLE 1 Test results Visual ASTM assessment D 1094,
after storage Ex. 4 Ex.5 Ex. 6 ASTM 5 min. + at Dose 1:1.sup.1) 2:1
3:1 D 1094 1 ppm -20.degree. C. [mg/kg] PIBA PE 1:3.sup.2) 2:3 3:3
SNH 2-PH 5 min. Dehazer.sup.3) for 7 days mod1 1150 250 200 100 300
300 4/3.sup.4) 2/3 Precipitation mod2 1150 250 200 100 300 300 4/2
0/1 Clear liquid mod3 1150 250 200 100 300 300 2/1 0/1 Clear liquid
mod4 1000 250 200 100 150 300 Solid mod5 1000 250 200 100 150 300
Clear liquid mod6 1000 250 200 100 150 300 Clear liquid mod7 850
250 200 100 150 150 Solid mod8 850 250 200 100 150 150
Precipitation mod9 850 250 200 100 150 150 Turbidity .sup.1)molar
ratio of fatty acid and alkanol amide reactants .sup.2)molar ratio
of functional groups of fatty acid and alkanol amide reactants
.sup.3)Dehazer: commercial product containing oxalkylated polymers
SNH = Solvent Naphta heavy 2-PH = 2-Propylheptanol .sup.4)Rating
scale according ASTM D 1094 interface/separation
[0126] This investigation clearly demonstrates that product of
Example 6 requires less solubilizer to achieve stable formulations.
At the same time products of Examples 5 and 6 are less critical in
the ASTM D 1094 test.
[0127] While the present invention was exemplified by making
reference to the reaction products obtained with two specific
reactants, a skilled reader will be enabled, guided by the general
teaching as provided herein, to perform the invention without undue
burden with other reactants of the general formulae I and II in
order to prepare superior fuel additives falling within the scope
of the present invention.
[0128] The disclosure of the citer prior art is incorporated by
reference.
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