U.S. patent application number 11/721524 was filed with the patent office on 2009-09-24 for hydrocarbyl succinic acid and hydrocarbylsuccinic acid derivatives as friction modifiers.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Arno Lange, Christian Lockemann, Dietmar Posselt, Ludwig Volkel.
Application Number | 20090235576 11/721524 |
Document ID | / |
Family ID | 34927748 |
Filed Date | 2009-09-24 |
United States Patent
Application |
20090235576 |
Kind Code |
A1 |
Volkel; Ludwig ; et
al. |
September 24, 2009 |
HYDROCARBYL SUCCINIC ACID AND HYDROCARBYLSUCCINIC ACID DERIVATIVES
AS FRICTION MODIFIERS
Abstract
The present invention relates to hydrocarbyl succinic acid and
hydrocarbylsuccinic acid derivatives as friction modifiers for
gasolines.
Inventors: |
Volkel; Ludwig;
(Limburgerhof, DE) ; Lange; Arno; (Bad Durkheim,
DE) ; Lockemann; Christian; (Mannheim, DE) ;
Posselt; Dietmar; (Heidelberg, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
34927748 |
Appl. No.: |
11/721524 |
Filed: |
December 12, 2005 |
PCT Filed: |
December 12, 2005 |
PCT NO: |
PCT/EP05/13304 |
371 Date: |
June 12, 2007 |
Current U.S.
Class: |
44/351 ;
44/404 |
Current CPC
Class: |
C10L 1/2225 20130101;
C10L 1/1883 20130101; C10L 1/2383 20130101; C10L 10/04 20130101;
C10L 1/2222 20130101; C10L 10/08 20130101; C10L 1/143 20130101;
C10L 1/1905 20130101; C10L 1/2387 20130101; C10L 1/198 20130101;
C10L 1/224 20130101; C10L 1/1985 20130101 |
Class at
Publication: |
44/351 ;
44/404 |
International
Class: |
C10L 1/18 20060101
C10L001/18; C10L 1/182 20060101 C10L001/182 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 13, 2004 |
EP |
04029480.3 |
Claims
1. The use of at least one hydrocarbyl succinic acid or hydrocarbyl
succinic acid derivative of the formula (I) ##STR00003## wherein
R.sup.1 is an aliphatic hydrocarbyl group containing less than 15%
quaternary carbon atoms, or is an araliphatic hydrocarbyl group; X
and Y are, independently of each other, OR.sup.2,
O.sup.-(M.sup.x+).sub.1/x or NR.sup.3R.sup.4 or X and Y together
form a group --O--; R.sup.2 is hydrogen, C.sub.1-C.sub.8-alkyl,
aryl or C.sub.1-C.sub.20-alkylaryl; R.sup.3 and R.sup.4 are,
independently of each other, hydrogen, C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-hydroxyalkyl,
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7, a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7, aryl or
C.sub.1-C.sub.20-alkylaryl; where R.sup.6, R.sup.7 and R.sup.8 are,
independently of each other, hydrogen, C.sub.1-C.sub.8-alkyl or
C.sub.2-C.sub.8-hydroxyalkyl; A is a C.sub.2-C.sub.4-alkylene
group; and y is 0 or an integer from 1 to 10; (M.sup.x+).sub.1/x a
metal equivalent, an ammonium cation [NH.sub.4].sup.+ or a
substituted ammonium cation equivalent; and x is 1, 2, 3 or 4 in
case (M.sup.x+).sub.1/x a metal equivalent, or is 1 in case
(M.sup.x+).sub.1/x an ammonium cation [NH.sub.4].sup.+ or is an
integer from 1 to 10 in case (M.sup.x+).sub.1/x is a substituted
ammonium cation equivalent, as friction modifying additive in a
gasoline.
2. The use as claimed in claim 1, where R.sup.1 is a linear or
branched C.sub.4-C.sub.40-alkenyl or C.sub.4-C.sub.40-alkyl group,
wherein at least 95% of the carbon atoms are no quaternary, or
R.sup.1 is a C.sub.1-C.sub.20-alkylaryl group.
3. The use as claimed in claim 2, where R.sup.1 is derived from an
.alpha.-alkene.
4. The use as claimed in claim 2, where R.sup.1 is derived from a
polyalkene obtained by oligo- or polymerization of at least one
C.sub.2-C.sub.8-alkene.
5. The use as claimed in claim 1, where R.sup.2 is hydrogen or
C.sub.1-C.sub.8-alkyl.
6. The use as claimed in claim 1, where R.sup.3 and R.sup.4 are,
independently of each other, hydrogen, C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-hydroxyalkyl,
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7, where R.sup.6, R.sup.7,
R.sup.8, A and y are as defined in claim 1
7. The use as claimed in claim 1, where (M.sup.x+).sub.1/x an
alkali metal cation, an alkaline earth metal equivalent, an
ammonium cation [NH.sub.4].sup.+ or a substituted ammonium cation
equivalent; x is 1 or 2 in case (M.sup.x+).sub.1/x an alkali metal
or alkaline earth metal equivalent, or is 1 in case
(M.sup.x+).sub.1/x is an ammonium cation [NH.sub.4].sup.+ or is an
integer from 1 to 10 in case (M.sup.x+).sub.1/x a substituted
ammonium cation equivalent
8. The use as claimed in claim 1, where X and Y are, independently
of each other, OR.sup.2, O.sup.-(M.sup.x+).sub.1/x, NR.sup.3R.sup.4
or X and Y together form a group --O--; R.sup.2 is hydrogen or
C.sub.1-C.sub.8-alkyl; R.sup.3 and R.sup.4 are, independently of
each other, hydrogen, C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-hydroxyalkyl,
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7; (M.sup.x+).sub.1/x is an alkali
metal cation, an alkaline earth metal equivalent, an ammonium
cation [NH.sub.4].sup.+ or a substituted ammonium cation
equivalent; x is 1 or 2 in case (M.sup.x+).sub.1/x an alkali metal
or alkaline earth metal equivalent, or is 1 in case
(M.sup.x+).sub.1/x is an ammonium cation [NH.sub.4].sup.+ or is an
integer from 1 to 10 in case (M.sup.x+).sub.1/x a substituted
ammonium cation equivalent; and R.sup.6, R.sup.7, R.sup.8-- A and y
are as defined in claim 1.
9. The use as claimed in claim 8, where X and Y are, independently
of each other, OH or O.sup.-(M.sup.x+).sub.1/x, or together form a
group --O--.
10. The use as claimed in claim 9, where X and Y are, independently
of each other, OH or O.sup.-(M.sup.x+).sub.1/x.
11. The use as claimed in claim 1, where the substituted ammonium
cation equivalent is derived from a monoamine
NR.sup.10R.sup.11R.sup.12, from a diamine of the formula
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7, or
from a polyamine of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7, where R.sup.10, R.sup.11, and R.sup.12
are, independently of each other, hydrogen, C.sub.1-C.sub.20-alkyl
or C.sub.2-C.sub.8-hydroxyalkyl, with the proviso that at least one
of the radicals R.sup.10, R.sup.11, and R.sup.12 is different from
hydrogen; R.sup.13 and R.sup.14 are, independently of each other,
hydrogen, C.sub.1-C.sub.8-alkyl or C.sub.2-C.sub.8-hydroxyalkyl; w
is an integer from 1 to 8; and R.sup.6, R.sup.7, R.sup.8 and A are
as defined in any of claims 1 to 4.
12. The use as claimed in claim 1, where the compound of formula
(I) is a hydrocarbyl succinic acid of the formula (I-1)
##STR00004## which is at least partially neutralized by a monoamine
NR.sup.10R.sup.11R.sup.12 or a diamine
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or a
polyamine of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7, where R.sup.10, R.sup.11, and R.sup.12
are, independently of each other, hydrogen, C.sub.1-C.sub.20-alkyl
or C.sub.2-C.sub.8-hydroxyalkyl, with the proviso that at least one
of the radicals R.sup.10, R.sup.11, and R.sup.12 is different from
hydrogen R.sup.13, and R.sup.14 are, independently of each other,
hydrogen, C.sub.1-C.sub.8-alkyl or C.sub.2-C.sub.8-hydroxyalkyl; w
is an integer from 1 to 8; and R.sup.1, R.sup.6, R.sup.7, R.sup.8
and A are as defined in any of claims 1 to 4.
13. The use as claimed in claim 1, where the compound of formula
(I) is a hydrocarbyl succinic acid of the formula (I-1)
##STR00005## where R.sup.1 is as defined in any of claims 1 to
4.
14. The use as claimed in claim 1, where the gasoline is additized
with the compound of formula (I) in an amount of from 10 to 300 mg
per kg of the gasoline.
15. The use as claimed in claim 1, in combination with at least one
further conventional fuel additive.
16. Gasoline composition containing a gasoline as major component
and at least one compound of the formula (I) as defined in claim 1
and optionally at least one further additive.
17. Additive concentrate, comprising at least one compound of the
formula (I) as defined in claim 1 and at least one diluent and
optionally at least one further additive.
18. A method for producing a gasoline composition with improved
friction properties, where a gasoline or a commercial gasoline
composition is additized with at least one compound of the formula
(I) as defined in claim 1.
19. The method according to claim 17 with the additive concentrate
of at least one diluent and optionally at least one further
additive.
Description
[0001] The present invention relates to hydrocarbyl succinic acid
and hydrocarbylsuccinic acid derivatives as friction modifiers for
gasolines.
BACKGROUND OF THE INVENTION
[0002] Carburettors and inlet systems of Otto engines, and also
injection systems for fuel proportioning, are subjected to
increasing load due to contamination caused by dust particles from
the air, unburned hydrocarbon residues from the combustion chamber
and crankcase breather gases passed to the carburettor.
[0003] These residues shift the air-to-fuel ratio during idling and
in the lower partial load region, so that the mixture becomes
leaner and combustion less complete and consequently the content of
unburned or partly burned hydrocarbons in the exhaust gas increases
and the gasoline consumption rises.
[0004] It is known to avoid these drawbacks by using fuel additives
for cleaning the valves and carburettors or injection systems of
Otto engines (cf e.g.: M. Rossenbeck in "Katalysatoren, Tenside,
Mineraloladditive", edited by J. Falbe, U. Hasserodt, page 223, G.
Thieme Verlag, Stuttgart 1978).
[0005] Furthermore, the problem of valve seat recession occurs in
the case of Otto engines of less recent design when fuelled with
unleaded gasolines. To counteract this, anti-valve seat recession
additives based on alkali metal or alkaline earth metal compounds
have been developed.
[0006] For trouble-free running, modern Otto engines require
automotive fuels having a complex set of properties which can only
be guaranteed when use is made of appropriate gasoline additives.
Such gasolines usually consist of a complex mixture of chemical
compounds and are characterized by physical parameters. The
interrelationship between gasolines and appropriate additives in
known fuel compositions is still unsatisfactory as regards their
detergent action or their pollution-abating properties and their
anti-valve seat recession action. Moreover, many of the known
additives act as emulsifying agents and thus promote the formation
of water/fuel emulsions. Disadvantageously, this promotes engine
wear and corrosion and may cause combustion problems.
[0007] WO 03/070860 describes a friction modifier of the formula
R.sup.1-L-N(R.sup.2R.sup.3), wherein R.sup.1 is a hydrocarbyl group
and L is a linker. Preferred compounds of that formula are
polyisobutenylsuccinimides, i.e. R.sup.1 is a polyisobutenyl
radical and L is a succinic acid derived group.
[0008] EP-A-1424322 describes polyisobutenylsuccinic acids or
derivatives thereof. The compounds are used, inter alia, as
detergents or dispersants for lube oil or fuels or as friction
modifiers for automatic transmission fluids and continuous variable
transmissions.
SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide a more
effective fuel/additive formulation. Moreover, the additive shall
have no or no significant emulsifying properties.
[0010] The inventors of the present invention found that this
object is achieved by the use of at least one hydrocarbyl succinic
acid or hydrocarbyl succinic acid derivative of the formula (I)
##STR00001##
wherein [0011] R.sup.1 is an aliphatic hydrocarbyl group containing
less than 15% quaternary carbon atoms, or is an araliphatic
hydrocarbyl group; [0012] X and Y are, independently of each other,
OR.sup.2, O.sup.-(M.sup.x+).sub.1/x or NR.sup.3R.sup.4 or X and Y
together form a group --O--; [0013] R.sup.2 is hydrogen,
C.sub.1-C.sub.8-alkyl, aryl or C.sub.1-C.sub.20-alkylaryl; [0014]
R.sup.3 and R.sup.4 are, independently of each other, hydrogen,
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-hydroxyalkyl,
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7, a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7 aryl or
C.sub.1-C.sub.20-alkylaryl; where [0015] R.sup.6, R.sup.7 and
R.sup.8 are, independently of each other, hydrogen,
C.sub.1-C.sub.8-alkyl or C.sub.2-C.sub.8-hydroxyalkyl; [0016] A is
a C.sub.2-C.sub.4-alkylene group; and [0017] y is 0 or an integer
from 1 to 10; [0018] (M.sup.x+).sub.1/x is a metal equivalent, an
ammonium cation [NH.sub.4].sup.+ or a substituted ammonium cation
equivalent; and [0019] x is 1, 2, 3 or 4 in case (M.sup.x+).sub.1/x
is a metal equivalent, or is 1 in case (M.sup.x+).sub.1/x is an
ammonium cation [NH.sub.4].sup.+ or is an integer from 1 to 10 in
case (M.sup.x+).sub.1/x is a substituted ammonium cation
equivalent, as friction modifying additive in a gasoline.
[0020] Preferably, compounds of formula (I) are used as friction
reducing agents in gasolines and Otto engines.
[0021] The invention is further related to a gasoline composition
containing a gasoline as major component and at least one compound
of the formula (I) as defined above and optionally at least one
further additive.
[0022] Moreover, the invention is related to an additive
concentrate, comprising at least one compound of the formula (I) as
defined above and at least one diluent and optionally at least one
further additive.
[0023] Finally, the invention is related to a method for producing
a gasoline composition with improved friction properties, where a
gasoline or a commercial gasoline composition is additized with at
least one compound of the formula (I) as defined above or with the
additive concentrate as defined above.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The organic moieties mentioned in the above definitions of
the variables are--like the term halogen--collective terms for
individual listings of the individual group members. The prefix
C.sub.n--C.sub.m indicates in each case the possible number of
carbon atoms in the group.
[0025] The term "aliphatic hydrocarbyl group containing less than
15% quaternary carbon atoms" denotes a branched or linear aliphatic
hydrocarbyl group where less than 15%, preferably less than 10% and
more preferably less than 5%, e.g. less than 3% or less than 2%, of
the carbon atoms are quaternary. An aliphatic hydrocarbyl group is
an acyclic radical essentially composed of carbon atoms and
hydrogen atoms, e.g. an alkyl, alkenyl or alkynyl group. A
quaternary carbon atom is a (sp.sup.3) carbon atom carrying four
radicals different from hydrogen. Alternatively, the term denotes
an araliphatic hydrocarbyl group, i.e. an aliphatic hydrocarbyl
group carrying at least one aryl substituent, e.g. an alkenylaryl
group or an alkylaryl group, where preferably less than 15%, more
preferably less than 10% and even more preferably less than 5%,
e.g. less than 3% or less than 2%, of the carbon atoms of the
aliphatic moiety are quaternary.
[0026] C.sub.8-C.sub.40-Alkenyl is a singly unsaturated
straight-chain or branched aliphatic hydrocarbon radical having
from 8 to 40 carbon atoms. Examples include octenyl, nonenyl,
decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,
elcosenyl, hencosenyl, docosenyl, tricosenyl, tetracosenyl,
pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,
squalenyl, constitutional isomers thereof, the higher homologs and
their constitutional isomers. Examples for constitutional isomers
of the aforementioned alkenyl radicals are polyalkenyl radicals
derived from oligomers and polymers of .alpha.-, .beta.-, .gamma.-,
.delta.-, etc. C.sub.3-C.sub.8-olefins, such as propene, 1- or
2-butene, 1- or 2-pentene, 1-, 2- or 3-hexene, 1-, 2- or 3-heptene
or 1-, 2-, 3- or 4-octene.
[0027] C.sub.4-C.sub.40-Alkenyl is a singly unsaturated
straight-chain or branched aliphatic hydrocarbon radical having
from 4 to 40 carbon atoms. Examples include the above-listed
examples for C.sub.8-C.sub.40-alkenyl and further butenyl,
pentenyl, hexenyl and heptenyl and constitutional isomers
thereof.
[0028] C.sub.8-C.sub.80-Alkenyl is a singly unsaturated
straight-chain or branched aliphatic hydrocarbon radical having
from 8 to 80 carbon atoms. Examples include the aforementioned
C.sub.8-C.sub.40-alkenyl radicals, constitutional isomers thereof,
the higher homologs and their constitutional isomers.
[0029] C.sub.4-C.sub.80-Alkenyl is a singly unsaturated
straight-chain or branched aliphatic hydrocarbon radical having
from 4 to 80 carbon atoms. Examples include the aforementioned
C.sub.8-C.sub.80-alkenyl radicals and further butenyl, pentenyl,
hexenyl and heptenyl and constitutional isomers thereof.
[0030] C.sub.10-C.sub.30-Alkenyl is a singly unsaturated
straight-chain or branched aliphatic hydrocarbon radical having
from 10 to 30 carbon atoms. Examples include decenyl, undecenyl,
dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,
heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, hencosenyl,
docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,
heptacosenyl, octacosenyl, nonacosenyl, squalenyl, constitutional
isomers thereof, the higher homologs and their constitutional
isomers.
[0031] C.sub.12-C.sub.16-Alkyl is a straight-chain or branched
alkyl group having from 12 to 16 carbon atoms. Examples include
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and their
constitutional isomers.
[0032] C.sub.10-C.sub.20-Alkyl is a straight-chain or branched
alkyl group having from 10 to 20 carbon atoms. Examples include
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their
constitutional isomers.
[0033] C.sub.8-C.sub.20-Alkyl is a straight-chain or branched alkyl
group having from 8 to 20 carbon atoms. Examples include octyl,
nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their
constitutional isomers.
[0034] C.sub.8-C.sub.40-Alkyl is a straight-chain or branched alkyl
group having from 8 to 40 carbon atoms. Examples include octyl,
nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,
octacosyl, nonacosyl, squalyl, constitutional isomers thereof, the
higher homologs and their constitutional isomers.
[0035] C.sub.4-C.sub.40-Alkyl is a straight-chain or branched alkyl
group having from 4 to 40 carbon atoms. Examples include the
aforementioned C.sub.8-C.sub.40-alkyl radicals and further butyl,
pentyl, hexyl and heptyl and constitutional isomers thereof.
[0036] C.sub.8-C.sub.80-Alkyl is a straight-chain or branched
hydrocarbon radical having from 8 to 80 carbon atoms. Examples
include the aforementioned C.sub.8-C.sub.40-alkyl radicals,
constitutional isomers thereof, the higher homologs and their
constitutional isomers.
[0037] C.sub.4-C.sub.80-Alkyl is a straight-chain or branched
hydrocarbon radical having from 4 to 80 carbon atoms. Examples
include the aforementioned C.sub.8-C.sub.80-alkyl radicals and
further butyl, pentyl, hexyl and heptyl and constitutional isomers
thereof.
[0038] C.sub.10-C.sub.30-Alkyl is a straight-chain or branched
hydrocarbon radical having from 10 to 30 carbon atoms. Examples
include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,
octacosyl, nonacosyl, squalyl, constitutional isomers thereof, the
higher homologs and their constitutional isomers.
[0039] C.sub.1-C.sub.4-Alkyl is a straight-chain or branched alkyl
group having from 1 to 4 carbon atoms. Examples of an alkyl group
are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl,
iso-butyl or tert-butyl. C.sub.1-C.sub.2 Alkyl is methyl or ethyl,
C.sub.1-C.sub.3 alkyl is additionally n-propyl or isopropyl.
[0040] C.sub.1-C.sub.8-Alkyl is a straight-chain or branched alkyl
group having from 1 to 8 carbon atoms. Examples include
C.sub.1-C.sub.4 alkyl as mentioned above and also pentyl,
1-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,
1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,
1-ethyl-2-methylpropyl, heptyl, octyl, and constitutional isomers
thereof, such as 2-ethylhexyl.
[0041] C.sub.1-C.sub.10-Alkyl is a straight-chain or branched alkyl
group having from 1 to 10 carbon atoms. Examples include
C.sub.1-C.sub.8-alkyl as mentioned above and also nonyl, decyl, and
constitutional isomers thereof.
[0042] C.sub.1-C.sub.20-Alkyl is a straight-chain or branched alkyl
group having from 1 to 20 carbon atoms. Examples include
C.sub.1-C.sub.8-alkyl as mentioned above and also nonyl, decyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, nonadecyl and eicosyl and constitutional
isomers thereof.
[0043] C.sub.2-C.sub.8-Hydroxyalkyl is a straight-chain or branched
alkyl group having from 2 to 8 carbon atoms, in particular 2 to 4
carbon atoms, wherein at least one, e.g. 1, 2, 3, or 4 of the
hydrogen atoms are replaced by a hydroxy group such as in
2-hydroxy-1-ethyl, 2- and 3-hydroxypropyl, 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 the like.
[0044] C.sub.2-C.sub.8-Alkylene is a linear or branched hydrocarbon
bridging group having 2, 3, 4, 5, 6, 7 or 8 carbon atoms, like
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, 1,7-heptylene, 1,8-octylene and
constitutional isomers thereof. C.sub.2-C.sub.4-Alkylene is a
linear or branched hydrocarbon bridging group having 2, 3 or 4
carbon atoms, like 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 and the like.
[0045] C.sub.1-C.sub.8-Alkoxy is a straight-chain or branched alkyl
group having from 1 to 8, in particular 1 to 4 carbon atoms, which
is bound to the remainder of the molecule via an oxygen atom.
Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
2-butoxy, iso-butoxy, tert.-butoxy pentyloxy, 1-methylbutoxy,
2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy,
1-ethylpropoxy, hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,
1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy,
4-methylpentyloxy, 1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy,
1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy,
3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy,
1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy,
1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy, heptyloxy,
octyloxy and their constitutional isomers.
[0046] Aryl denotes a carbocyclic C.sub.6-C.sub.14-aromatic radical
like phenyl, naphthyl, anthracenyl or phenantrenyl, which
optionally carries 1 to 3 substituents selected from halogen, OH,
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-alkyl, nitro, cyano and an
aryl radical.
[0047] Alkylaryl is an alkyl group which carries at least one aryl
radical and is in particular a C.sub.1-C.sub.20-alkylaryl group.
C.sub.1-C.sub.20-alkylaryl denotes a C.sub.1-C.sub.20-alkyl group
which carries at least one aryl radical. Examples thereof are
benzyl, 1- and 2-phenylethyl, 1-, 2- and 3-phenylpropyl, 1-, 2-, 3-
and 4-phenylbutyl, 1-, 2-, 3-, 4- and 5-phenylpentyl, 1-, 2-, 3-,
4-, 5- and 6-phenylhexyl, 1-, 2-, 3-, 4-, 5-, 6- and
7-phenylheptyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-phenyloctyl, 1-,
2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-phenylnonyl, 1-, 2-, 3-, 4-, 5-,
6-, 7-, 8-, 9- and 10-phenyldecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-,
9-, 10 and 11-phenylundecyl, phenyldodecyl, phenyltridecyl,
phenyltetradecyl, phenylpentadecyl, phenylhexadecyl,
phenylheptadecyl, phenyloctadecyl, phenylnonadecyl and
phenyleicosyl and constitutional isomers thereof.
[0048] C.sub.1-C.sub.10-alkylaryl denotes a C.sub.1-C.sub.10-alkyl
group which carries at least one aryl radical. Examples thereof are
benzyl, 1- and 2-phenylethyl, 1-, 2- and 3-phenylpropyl, 1-, 2-, 3-
and 4-phenylbutyl, 1-, 2-, 3-, 4- and 5-phenylpentyl, 1-, 2-, 3-,
4-, 5- and 6-phenylhexyl, 1-, 2-, 3-, 4-, 5-, 6- and
7-phenylheptyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-phenyloctyl, 1-,
2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-phenylnonyl, and 1-, 2-, 3-, 4-,
5-, 6-, 7-, 8-, 9- and 10-phenyldecyl, and constitutional isomers
thereof.
[0049] Alkenylaryl is an alkenyl group which carries at least one
aryl radical and is in particular a C.sub.1-C.sub.20-alkenylaryl
group. C.sub.1-C.sub.20-alkenylaryl denotes a
C.sub.1-C.sub.20-alkenyl group which carries at least one aryl
radical.
[0050] The metal equivalent (M.sup.x+).sub.1/x is a metal cation
carrying 1, 2, 3 or 4 positive charges and respectively formally
equivalating 1, 2, 3 or 4 anions O.sup.- (or, more precisely,
COO.sup.-), or (M.sup.x+).sub.1/x is an ammonium cation
NH.sub.4.sup.+ which formally equivalates 1 anion O.sup.- (or, more
precisely, COO.sup.-) or (M.sup.x+).sub.1/x is a substituted
ammonium cation and respectively formally equivalating 1 to 10
anions O.sup.- (or, more precisely, COO.sup.-).
[0051] The term "substituted ammonium cation" denotes a cation
derived from a monoamine NR.sup.10R.sup.11R.sup.12, where the
radicals R.sup.10, R.sup.11 and R.sup.12 are, independently of each
other, selected from hydrogen, aliphatic hydrocarbyl which is
optionally substituted by hydroxyl groups, araliphatic hydrocarbyl
and aryl, with the proviso that at least one of the radicals
R.sup.10, R.sup.11 and R.sup.12 is not hydrogen, or from a diamine
or a polyamine, where the amino function(s) may be substituted by
aliphatic hydrocarbyl groups which are optionally substituted by
hydroxyl groups; araliphatic hydrocarbyl groups and/or aryl groups.
The cation generally results from the addition of protons H.sup.+
to at least part of the basic nitrogen atoms present in the
amine.
[0052] The term halogen denotes in each case fluorine, bromine,
chlorine or iodine, in particular fluorine, chlorine or
bromine.
[0053] With respect to the use according to the invention of the
compounds of formula I and to the fuel composition and the additive
concentrate containing the compound of formula I, preference is
given to the following meanings of the substituents and variables
(X, Y, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
A, M, y, w, x), in each case on their own or in combination:
[0054] Preferably, R.sup.1 is a linear or branched aliphatic
hydrocarbyl group containing 4 to 80, e.g. 8 to 80, preferably 4 to
40, more preferably 8 to 40 and in particular 10 to 30 carbon
atoms. Preferred aliphatic hydrocarbyl groups are alkyl, e.g.
C.sub.4-C.sub.80-alkyl, such as C.sub.8-C.sub.80-alkyl, preferably
C.sub.4-C.sub.40-alkyl, more preferably C.sub.8-C.sub.40-alkyl, in
particular C.sub.10-C.sub.30-alkyl, and alkenyl, e.g.
C.sub.4-C.sub.80-alkenyl, such as C.sub.8-C.sub.80-alkenyl,
preferably C.sub.4-C.sub.40-alkenyl, more preferably
C.sub.8-C.sub.40-alkenyl, in particular
C.sub.10-C.sub.30-alkenyl.
[0055] Alternatively, R.sup.1 is preferably a
C.sub.1-C.sub.20-alkylaryl group, more preferably a
C.sub.1-C.sub.10-alkylaryl group. Suitable alkylaryl groups are
listed above.
[0056] However, in a more preferred embodiment, R.sup.1 is a linear
or branched aliphatic hydrocarbyl group, such as an alkyl group or
an alkenyl group, as defined above.
[0057] In an even more preferred embodiment, R.sup.1 is a linear or
branched alkenyl group, preferably a C.sub.4-C.sub.80-alkenyl
group, such as a C.sub.8-C.sub.80-alkenyl group, more preferably a
C.sub.4-C.sub.40-alkenyl group, especially a
C.sub.8-C.sub.40-alkenyl group and in particular a
C.sub.10-C.sub.30-alkenyl group.
[0058] In a particularly preferred embodiment, R.sup.1 is derived
from an alkene, preferably from a C.sub.4-C.sub.80-alkene, e.g. a
C.sub.8-C.sub.80-alkene, more preferably from a
C.sub.4-C.sub.40-alkene, e.g. a C.sub.8-C.sub.40-alkene, and in
particular from a C.sub.10-C.sub.30-alkene. The alkene may be
linear or branched (with the above proviso), and the olefinic
double bond may be in a terminal or internal position. Preferred
alkenes are .alpha.-alkenes (i.e. the olefinic double bond is in a
terminal position), e.g. .alpha.-C.sub.4-C.sub.40-alkenes, such as
.alpha.-C.sub.8-C.sub.80-alkenes, preferably
.alpha.-C.sub.4-C.sub.40-alkenes, e.g.
.alpha.-C.sub.8-C.sub.40-alkenes, and more preferably
.alpha.-C.sub.10-C.sub.30-alkenes. In a more preferred embodiment,
the alkenes are linear .alpha.-alkenes.
[0059] Alternatively, R.sup.1 is derived from a polyalkene, which
is obtained by oligo- or polymerization of an alkene. Preferably,
the polyalkene is a C.sub.4-C.sub.80-polyalkene, e.g. a
C.sub.8-C.sub.80-polyalkene, more preferably a
C.sub.4-C.sub.40-polyalkene, e.g. a C.sub.8-C.sub.40-polyalkene,
and in particular a C.sub.10-C.sub.30-polyalkene. The alkene from
which the polyalkene is derived may be linear or branched.
Preferably, the alkene is selected from C.sub.2-C.sub.8-alkenes,
such as ethylene, propene, 1- or 2-butene, 1- or 2-pentene, 1-, 2-
or 3-hexene, 1-, 2- or 3-heptene and 1-, 2-, 3- or 4-octene or
constitutional or stereochemical isomers thereof. The polyalkene
may also be obtained from oligo- or polymerization of an alkene
mixture, especially of a technical mixture of olefins such as
obtained in industrial processes, e.g. in cracking processes, with
the proviso that not more than 20% by weight, preferably not more
than 10% by weight, more preferably not more than 5% by weight,
based on the total weight of the alkene mixture, of the alkenes
contained in the mixture are alkenes wherein one or both carbon
atoms of the olefinic double bond carry two substituents different
from hydrogen. A suitable technical mixture is e.g. a C.sub.4-cut
comprising 1-butene, 2-butene and isobutene, wherein isobutene is
contained in an amount of not more than 20% by weight, preferably
not more than 10% by weight, more preferably not more than 5% by
weight, based on the total weight of the composition.
[0060] In a special embodiment, R.sup.1 is derived from dodecene,
tridecene, tetradecene, pentadecene, hexadecene, heptadecene,
octadecene, nonadecene, eicosene, or the higher homologs.
Preferably, the olefinic double bond in said alkenes is in the
.alpha.-position and/or the alkenes are linear.
[0061] In an alternative special embodiment, R.sup.1 is derived
from the tri-, tetra- or pentamers of butene, hexene or octene.
[0062] In an alternative preferred embodiment, the compound of
formula (I) is a mixture of compounds of formula (I) with different
radicals R.sup.1, where the mixture contains not more than 10% by
weight, preferably not more than 5% by weight, more preferably not
more than 3% by weight of compounds of formula (I) wherein R.sup.1
is a C.sub.4-C.sub.7-hydrocarbyl group, e.g. a
C.sub.4-C.sub.7-alkyl group or a C.sub.4-C.sub.7-alkenyl group.
[0063] In the definition of X and Y, R.sup.2 is preferably hydrogen
or C.sub.1-C.sub.8-alkyl. In a particular embodiment, R.sup.2 is
hydrogen or C.sub.1-C.sub.4-alkyl. Especially, R.sup.2 is
hydrogen.
[0064] Preferably, R.sup.3 and R.sup.4 are, independently of each
other, hydrogen, C.sub.1-C.sub.8-alkyl, e.g. C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.8-hydroxyalkyl, e.g. C.sub.2-C.sub.4-hydroxyalkyl,
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7, e.g.
C.sub.2-C.sub.4-alkylene-NR.sup.6R.sup.7, or a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7, where R.sup.6, R.sup.7,
R.sup.8, A and y are as defined above. Preferably, R.sup.6,
R.sup.7, R.sup.8, A and y are as defined below. In a particular
embodiment, R.sup.3 and R.sup.4 are hydrogen or
C.sub.1-C.sub.4-alkyl. Especially, R.sup.3 and R.sup.4 are
hydrogen.
[0065] Preferably, R.sup.8 is hydrogen or C.sub.1-C.sub.8-alkyl. In
a more preferred embodiment, R.sup.8 is hydrogen or
C.sub.1-C.sub.4-alkyl, especially hydrogen, methyl or ethyl and in
particular hydrogen.
[0066] In a preferred embodiment, R.sup.6 and R.sup.7 are,
independently of each other, hydrogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-hydroxyalkyl. In a more preferred embodiment,
R.sup.6 and R.sup.7 are, independently of each other, hydrogen or
C.sub.1-C.sub.4-alkyl, especially hydrogen, methyl or ethyl and in
particular hydrogen.
[0067] A is preferably 1,2-ethylene (--(CH.sub.2).sub.2--),
1,2-propylene (--CH.sub.2--CH(CH.sub.3)-- or
--CH(CH.sub.3)--CH.sub.2--), 1,3-propylene (--(CH.sub.2).sub.3--)
or 1,4-butylene (--(CH.sub.2).sub.4--). In particular, A is
1,2-ethylene.
[0068] y is preferably 0, 1, 2, 3, 4 or 5, more preferably 1, 2, 3
or 4.
[0069] Preferably, (M.sup.x+).sub.1/x is an alkali metal
equivalent, an alkaline earth metal equivalent, an ammonium cation
NH.sub.4.sup.+ or a substituted ammonium cation. Correspondingly, x
is 1 if M is an alkali metal or an ammonium cation NH.sub.4.sup.+
and x is 2 if M is an alkaline earth metal. Preferred alkali metals
are lithium, sodium and potassium and consequently, preferred
alkali metal equivalents are Li.sup.+, Na.sup.+ and K.sup.+.
Preferred alkaline earth metals are magnesium and calcium and
consequently, preferred alkaline earth metal equivalents are 1/2
Mg.sup.2+ and 1/2 Ca.sup.2+.
[0070] In case (M.sup.x+).sub.1/x is a substituted ammonium cation,
this is preferably derived from a monoamine
NR.sup.10R.sup.11R.sup.12, from a diamine of the formula
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or from
a polyamine of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7,
where [0071] R.sup.10, R.sup.11, and R.sup.12 are, independently of
each other, hydrogen, C.sub.1-C.sub.20-alkyl or
C.sub.2-C.sub.8-hydroxyalkyl, with the proviso that at least one of
the radicals R.sup.10, R.sup.11, and R.sup.12 is different from
hydrogen; [0072] R.sup.13 and R.sup.14 are, independently of each
other, hydrogen, C.sub.1-C.sub.8-alkyl or
C.sub.2-C.sub.8-hydroxyalkyl; w is an integer from 1 to 8; and
R.sup.6, R.sup.7, R.sup.8 and A and their preferred embodiments are
as defined above.
[0073] Suitable and preferred amines from which the cations are
derived are listed below.
[0074] The ammonium cation derived from the above amines generally
results from the addition of a cation, preferably of a proton
H.sup.+ to at least part of the basic nitrogen atoms present in the
amine. Consequently, the ammonium cation derived from the monoamine
preferably has the formula [NHR.sup.10R.sup.11R.sup.12].sup.+;
preferably, the ammonium cation derived from the diamine is either
a monocation of the formula
[NHR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7].sup.+
or
[NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NHR.sup.6R.sup.7].sup.+
or a dication of the formula
[NHR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NHR.sup.6R.sup.7].sup.2+;
and preferably, the ammonium cation derived from the polyamine is
either a monocation or a polycation having from 2 to (w+2) positive
charges, depending on the number of protonated nitrogen atoms in
the molecule.
[0075] Preferably, in the monoamine NR.sup.10R.sup.11R.sup.12,
R.sup.10, R.sup.11 and R.sup.12 are, independently of each other,
hydrogen, C.sub.8-C.sub.20-alkyl or C.sub.2-C.sub.8-hydroxyalkyl,
more preferably hydrogen, C.sub.8-C.sub.20-alkyl or
C.sub.2-C.sub.4-hydroxyalkyl, even more preferably hydrogen,
C.sub.10-C.sub.20-alkyl or C.sub.2-C.sub.4-hydroxyalkyl, in
particular hydrogen, C.sub.12-C.sub.16-alkyl or
C.sub.2-C.sub.4-hydroxyalkyl, with the proviso that at least one of
the radicals R.sup.10, R.sup.11 and R.sup.12 is not hydrogen.
[0076] Preferred radicals R.sup.13 and R.sup.14 are hydrogen,
C.sub.1-C.sub.4-alkyl or C.sub.2-C.sub.4-hydroxyalkyl, more
preferred being hydrogen and C.sub.1-C.sub.4-alkyl. In the cations
derived from di- and poly-amines, preferably at least 2 of the
radicals R.sup.13, R.sup.14, R.sup.6 and R.sup.7 are hydrogen. More
preferably, at least one of the radicals R.sup.13 and R.sup.14 and
least one of the radicals R.sup.6 and R.sup.7 is hydrogen. In
particular, all four radicals R.sup.6, R.sup.7, R.sup.13 and
R.sup.14 are hydrogen. Especially, R.sup.8 is also hydrogen.
[0077] Preferably, M.sup.x+ is a substituted ammonium cation.
[0078] In a more preferred embodiment, M.sup.x+ is a substituted
ammonium cation derived from a diamine of the formula
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or from
a polyamine of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7, where R.sup.6, R.sup.7, R.sup.8, R.sup.13,
R.sup.14, A and w and there preferred embodiments are as defined
above.
[0079] In an alternatively more preferred embodiment, M.sup.x+ is a
substituted ammonium cation derived from a monoamine
NR.sup.10R.sup.11R.sup.12, where at least one of the radicals
R.sup.10, R.sup.11 and R.sup.12 is C.sub.8-C.sub.20-alkyl,
preferably C.sub.10-C.sub.20-alkyl, more preferably
C.sub.12-C.sub.16-alkyl, and the remaining radical(s) is/are
hydrogen. In particular, one or two, preferably one, of the
radicals R.sup.10, R.sup.11 and R.sup.12 is C.sub.8-C.sub.20-alkyl,
preferably C.sub.10-C.sub.20-alkyl, more preferably
C.sub.12-C.sub.16-alkyl, and the remaining radical(s) are
hydrogen.
[0080] In an alternatively more preferred embodiment, M.sup.x+ is a
substituted ammonium cation derived from a monoamine
NR.sup.10R.sup.11R.sup.12, where R.sup.10 is
C.sub.2-C.sub.8-hydroxyalkyl, preferably
C.sub.2-C.sub.4-hydroxyalkyl, R.sup.11 is
C.sub.2-C.sub.8-hydroxyalkyl, e.g. C.sub.2-C.sub.4-hydroxyalkyl, or
C.sub.1-C.sub.8-alkyl, e.g. C.sub.1-C.sub.4-alkyl, and R.sup.12 is
C.sub.2-C.sub.8-hydroxyalkyl, e.g. C.sub.2-C.sub.4-hydroxyalkyl,
C.sub.1-C.sub.8-alkyl, e.g. C.sub.1-C.sub.4-alkyl, or hydrogen.
[0081] In case X and Y together form a group --O--, the compound of
formula (I) is a hydrocarbyl-substituted succinic acid
anhydride.
[0082] In a particularly preferred embodiment, X and Y are,
independently of each other, OH or O.sup.-(M.sup.x+).sub.1/x, or X
and Y together form a group --O--. Preferably, (M.sup.x+).sub.1/x
is an alkali or alkaline earth metal cation or more preferably an
ammonium cation NH.sub.4.sup.+ or a substituted ammonium cation as
defined above. In an even more preferred embodiment,
(M.sup.x+).sub.1/x is an ammonium cation derived from substituted
amines, preferably from the above-described monoamines, diamines or
polyamines and in particular from the above-described diamines or
polyamines. Examples of suitable substituted amines are listed
below.
[0083] In an even more preferred embodiment, Y are, independently
of each other, OH or O.sup.-(M.sup.x+).sub.1/x, where M and x and
their preferred embodiments are as defined above. Preferably,
(M.sup.x+).sub.1/x is an alkali or alkaline earth metal cation or
more preferably an ammonium cation NH.sub.4.sup.+ or a substituted
ammonium cation as defined above. In an even more preferred
embodiment, (M.sup.x+).sub.1/x an ammonium cation derived from
substituted amines, preferably from the above-described monoamines,
diamines or polyamines and in particular from the above-described
diamines or polyamines. Examples of suitable substituted amines are
listed below.
[0084] In particular embodiment, the compound of formula (I) is a
hydrocarbyl succinic acid of the formula (I-1)
##STR00002##
which is at least partially neutralized by a monoamine
NR.sup.10R.sup.11R.sup.12 or a diamine
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or a
polyamine of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7, where [0085] R.sup.10, R.sup.11, and
R.sup.12 are, independently of each other, hydrogen,
C.sub.1-C.sub.20-alkyl or C.sub.2-C.sub.8-hydroxyalkyl; [0086]
R.sup.13 and R.sup.14 are, independently of each other, hydrogen,
C.sub.1-C.sub.8-alkyl or C.sub.2-C.sub.8-hydroxyalkyl; w is an
integer from 1 to 8; and R.sup.1, R.sup.6, R.sup.7, R.sup.8 and A
and their preferred embodiments are as defined above.
[0087] In the monoamine NR.sup.10R.sup.11R.sup.12, the radicals
R.sup.10, R.sup.11 and R.sup.12 are, independently of each other,
preferably hydrogen, C.sub.8-C.sub.20-alkyl or
C.sub.2-C.sub.8-hydroxyalkyl, more preferably hydrogen,
C.sub.8-C.sub.2-alkyl or C.sub.2-C.sub.4-hydroxyalkyl, even more
preferably hydrogen, C.sub.10-C.sub.20-alkyl or
C.sub.2-C.sub.4-hydroxyalkyl, in particular hydrogen,
C.sub.12-C.sub.16-alkyl or C.sub.2-C.sub.4-hydroxyalkyl, with the
proviso that at least one of the radicals R.sup.10, R.sup.11 and
R.sup.12 is not hydrogen.
[0088] In the diamine or in the polyamine, R.sup.6, R.sup.7,
R.sup.13 and R.sup.14 are, independently of each other, preferably
hydrogen, C.sub.1-C.sub.4-alkyl, or C.sub.2-C.sub.4-hydroxyalkyl.
More preferably, R.sup.6, R.sup.7, R.sup.13 and R.sup.14 are,
independently of each other, hydrogen or C.sub.1-C.sub.4-alkyl. In
an even more preferred embodiment, at least two of the radicals
R.sup.13, R.sup.14, R.sup.6 and R.sup.7 are hydrogen. More
preferably, at least one of the radicals R.sup.13 and R.sup.14 and
least one of the radicals R.sup.6 and R.sup.7 is hydrogen. In
particular, all four radicals R.sup.6, R.sup.7, R.sup.13 and
R.sup.14 are hydrogen. Especially, R.sup.8 is also hydrogen.
[0089] Examples for useful monoamines NR.sup.10R.sup.11R.sup.12,
wherein R.sup.10, R.sup.11 and R.sup.12 are hydrogen,
C.sub.1-C.sub.20-alkyl or C.sub.2-C.sub.8-hydroxyalkyl, are ammonia
and primary, secondary or tertiary monoamines, such as methylamine,
dimethylamine, trimethylamine, ethylamine, diethylamine,
triethylamine, ethanolamine, diethanolamine, triethanolamine,
ethanolethylamine, ethanoldiethylamine, ethanolpropylamine,
ethanoldipropylamine, ethanolbutylamine, ethanoldibutylamine,
propylamine, dipropylamine, tripropylamine, propanolamine,
dipropanolamine, tripropanolamine, propanolethylamine,
propanoldiethylamine, propanolpropylamine, propanoldipropylamine,
propanolbutylamine, propanoldibutylamine, isopropylamine,
diisopropylamine, triisopropylamine, ethyldlisopropylamine,
butylamine, dibutylamine, tributylamine, isobutylamine,
diisobutylamine, tert-butylamine, di-tert-butylamine, pentylamine,
hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine,
decylamine, undecylamine, dodecylamine, tridecylamine,
tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine,
octadecylamine, nonadecylamine, eicosylamine and the like. Mixtures
of amines are also suitable. Preferred monoamines are the above
alkanolamines and C.sub.8-C.sub.20-alkylamines, such as octylamine,
2-ethylhexylamine, nonylamine, decylamine, undecylamine,
dodecylamine, tridecylamine, tetradecylamine, pentadecylamine,
hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine and
eicosylamine.
[0090] Examples for diamines of the formula
NR.sup.13R.sup.14--C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 and for
polyamines of the formula NR.sup.13R.sup.14 A-NR.sup.8
.sub.wA-NR.sup.6R.sup.7 are ethylenediamine, diethylentriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, propylenediamine, dipropylentriamin,
tripropylenetetramine, tetrapropylenepentamine,
pentapropylenehexamine, butylenediamine, dibutylenetriamine,
tributylenetetramine, tetrabutylenepentamine,
pentabutylenehexamine, pentylenedlamine, hexylenediamine,
heptylenediamine, octylenediamine,
N,N-dimethylethylene-1,2-diamine,
N,N'-dimethylethylene-1,2-diamine, N,N-diethylethylene-1,2-diamine,
N,N'-diethylethylene-1,2-diamine,
N,N-diethanolethylene-1,2-diamine,
N,N'-diethanolethylene-1,2-diamine,
N,N-dipropylethylene-1,2-diamine,
N,N'-dipropylethylene-1,2-diamine,
N,N-dipropanolethylene-1,2-diamine,
N,N'-dipropanolethylene-1,2-diamine,
N,N-dimethylpropylene-1,3-diamine,
N,N'-dimethylpropylene-1,3-diamine,
N,N-diethylpropylene-1,3-dlamine,
N,N'-diethylpropylene-1,3-diamine,
N,N-diethanolpropylene-1,3-diamine,
N,N'-diethanolpropylene-1,3-diamine,
N,N-dipropylpropylene-1,3-diamine,
N,N'-dipropylpropylene-1,3-diamine,
N,N-dipropanolpropylene-1,3-dlamine,
N,N'-dipropanolpropylene-1,3-diamine,
N,N-dimethylbutylene-1,4-diamine,
N,N'-dimethylbutylene-1,4-diamine, N,N-diethylbutylene-1,4-diamine,
N,N'-diethylbutylene-1,4-dlamine,
N,N-diethanolbutylene-1,4-diamine,
N,N'-diethanolbutylene-1,4-diamine,
N,N-dipropylbutylene-1,4-diamine,
N,N'-dipropylbutylene-1,4-diamine,
N,N-dipropanolbutylene-1,4-diamine,
N,N'-dipropanoibutylene-1,4-diamine,
N,N-dimethylpentylene-1,5-diamine,
N,N'-dimethylpentylene-1,5-diamine,
N,N-diethylpentylene-1,5-diamine,
N,N'-diethylpentylene-1,5-diamine,
N,N-diethanolpentylene-1,5-diamine,
N,N'-diethanolpentylene-1,5-diamine,
N,N-dipropylpentylene-1,5-diamine,
N,N'-dipropylpentylene-1,5-diamine,
N,N-dipropanolpentylene-1,5-diamine,
N,N'-dipropanolpentylene-1,5-diamine,
N,N-dimethylhexylene-1,6-diamine,
N,N'-dimethylhexylene-1,6-diamine, N,N-diethylhexylene-1,6-diamine,
N,N'-diethylhexylene-1,6-diamine,
N,N-diethanolhexylene-1,6-diamine,
N,N'-diethanolhexylene-1,6-diamine,
N,N-dipropylhexylene-1,6-diamine,
N,N'-dipropylhexylene-1,6-dlamine,
N,N-dipropanolhexylene-1,6-diamine,
N,N'-dipropanolhexylene-1,6-diamine,
bis[2-(N,N-dimethylamino)ethyl]amine,
bis[2-(N,N-diethylamino)ethyl]amine,
bis[2-(N,N-dipropylamino)ethyl]amine,
bis[3-(N,N-dimethylamino)propyl]amine,
bis[3-(N,N-diethylarhino)propyl]amine,
bis[3-(N,N-dipropylamino)propyl]amine,
bis[4-(N,N-dimethylamino)butyl]amine,
bis[4-(N,N-diethylamino)butyl]amine,
bis[4-(N,N-dipropylamino)butyl]amine,
bis[5-(N,N-dimethylamino)pentyl]amine,
bis[5-(N,N-diethylamlno)pentyl]amine,
bis[5-(N,N-dipropylamino)pentyl]amine,
bis[6-(N,N-dimethylamino)hexyl]amine,
bis[6-(N,N-diethylamino)hexyl]amine,
bis[6-(N,N-dipropylamino)hexyl]amine and the like. Such polyamines
are described in Kirk-Othmers "Encyclopedia of Chemical
Technology", 2.sup.nd edition, volume 7, pages 22 to 37,
Interscience Publishers, New York (1965, chapter "Ethyleneamines"),
which is hereby fully incorporated by reference.
[0091] In an alternative particular embodiment of the invention,
the compound of formula (I) is a hydrocarbyl succinic acid of the
formula (I-1).
[0092] Processes for preparing hydrocarbyl-substituted succinic
acids and their derivatives are well known. For instance, the
German patent application DE-A-10123553.4 describes the preparation
of a polyalkenyl-substituted carboxylic acid or a derivative
thereof by the reaction of a polyalkene with a monounsaturated acid
or its derivative, in which the polyalkene adds in an ene reaction
to the double bond of the acid component. If desired, the obtained
alkenyl-substituted succinic acid derivative may then be converted
into the corresponding alkyl-substituted succinic acid derivative
by hydrogenating the olefinic double bond by known methods.
[0093] Processes for converting the obtained
hydrocarbyl-substituted succinic acid or its derivative into
another derivative are also well known. For instance, the acide
halide can be prepared by reacting the anhydride with halogenation
agents, such as SOCl.sub.3, PCl.sub.3 or PBr.sub.3. The acid halide
can then be converted into the mono- or diester by reacting with
the corresponding amount of an alcohol R.sup.2OH. The acid salts
can be prepared e.g. by hydrolyzing the anhydride with a metal
hydroxide or by reacting the acid with an amine. The hydrocarbyl
succinic amides, i.e. compounds of formula (I), wherein X and/or Y
are a group NR.sup.3R.sup.4 and R.sup.3 and/or R.sup.4 are
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-hydroxyalkyl, a group
C.sub.2-C.sub.8-alkylene-NR.sup.6R.sup.7 or a group of the formula
A-NR.sup.8 .sub.yA-NR.sup.6R.sup.7, can be prepared by reacting a
suitable hydrocarbyl succinic acid derivative with the
above-described amines under appropriate conditions known in the
art.
[0094] Preferably, the gasoline is additized with the compound of
formula (I) in an amount of from 10 to 300, more preferably from 20
to 200, in particular from 25 to 150 mg per kg of the gasoline.
[0095] Preferably, the compound of formula (I) is used in the
gasoline in combination with at least one further conventional fuel
additive. Conventional fuel additives are, e.g., detergent
additives, carrier oils, corrosion inhibitors, antioxidants,
antistatics, markers, etc., and mixtures thereof.
A) Detergent Additives
[0096] Additives having a detergent action or an anti-valve seat
recession action are e.g. compounds which contain at least one
hydrophobic hydrocarbon group having a number-average molecular
weight (M.sub.n) of from 85 to 20,000 and at least one polar group
selected from [0097] (a) monoamino or polyamino groups containing
up to 6 nitrogen atoms, of which at least one has alkaline
properties, [0098] (b) nitro groups, optionally combined with
hydroxyl groups, [0099] (c) hydroxyl groups combined with monoamino
or polyamino groups, in which at least one nitrogen atom has
alkaline properties, [0100] (d) carboxylic acid groups or the
alkali metal or alkaline earth metal salts thereof, [0101] (e)
sulfo groups or the alkali metal or alkaline earth metal salts
thereof, [0102] (f) polyoxy-(C.sub.2-C.sub.4 alkylene) groups which
are terminated by hydroxyl groups, by monoamino or polyamino
groups, in which at least one nitrogen atom has alkaline
properties, or by carbamate groups, [0103] (g) carboxylate groups,
[0104] (h) groups derived from succinic anhydride and containing
hydroxyl and/or amino and/or amido and/or imido groups, which are
different from compounds of formula (I); and [0105] (i) groups
produced by Mannich reaction of substituted phenols with aldehydes
and mono- or poly-amines.
[0106] The hydrophobic hydrocarbon group in the additives, which
provides sufficient solubility In the fuel, has a number-average
molecular weight (M.sub.n) of from 85 to 20,000, preferably from
113 to 10,000 and more preferably from 300 to 5000. Typical
hydrophobic hydrocarbon groups, particularly in conjunction with
the polar groups (a), (c), (h) and (i), are polypropenyl,
polybutenyl and polyisobutenyl radicals having molecular weights
M.sub.n of from 300 to 5000, preferably from 500 to 2500 and more
preferably from 750 to 2250.
[0107] The following examples of individual fuel additives having a
detergent action or an anti-valve seat recession effect are
mentioned by way of example.
[0108] Additives containing monoamino or polyamino groups (a) are
preferably polyalkene monoamines or polyalkene polyamines based on
polypropylene or highly reactive (ie containing predominantly
terminal double bonds--mostly in the - and -positions) or
conventional (ie containing predominantly centered double bonds)
polybutylene or polyisobutylene having a molecular weight M.sub.n
of from 300 to 5000. Such additives based on highly reactive
polyisobutylene which can be prepared from the polyisobutylene
containing up to 20 wt % of n-butylene units, by hydroformylation
and reductive amination with ammonia, monoamines or polyamines such
as dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or tetrethylenepentamine, are disclosed, in
particular, in EP-A 244,616. If the synthesis of the additives is
based on polybutylene or polyisobutylene having predominantly
centered double bonds (mostly in the and .gamma. positions) as
starting materials, an obvious choice is the synthesis method
involving chlorination and subsequent amination, or oxidation of
the double bond with air or ozone to form the carbonyl or carboxyl
compound, with subsequent amination under reductive (hydrogenating)
conditions. This amination may be carried out using the same amines
as mentioned above for the reductive amination of hydroformylated,
highly reactive polyisobutylene. Corresponding additives based on
polypropylene are described, in particular, in WO-A 94/24231.
[0109] Further preferred additives containing monoamino groups (a)
are the hydrogenation products of the reaction products of
polyisobutylenes having an average degree of polymerization P of
from 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides
and oxygen, as described, in particular, in WO-A 97/03946.
[0110] Further preferred additives containing monoamino groups (a)
are the compounds produced from polyisobutylene epoxides by
reaction with amines followed by dehydration and reduction of the
amino alcohols, as described, in particular, in DE-A 196 20
262.
[0111] Additives containing nitro groups, optionally combined with
hydroxyl groups (b), are preferably reaction products of
polyisobutylenes having an average degree of polymerization P of
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 usually
mixtures of pure nitropolyisobutanes (eg
.alpha.,.beta.-dinitropolyisobutane) and mixed
hydroxynitropolyisobutanes (eg
.alpha.-nitro-.beta.-hydroxypolyisobutane).
[0112] Additives containing hydroxyl groups combined with monoamino
or polyamino groups (c) are in particular reaction products of
polyisobutylene epoxides, obtainable from polyisobutylene
preferably containing predominantly terminal double bonds and
having a molecular weight M.sub.n of from 300 to 5000, with ammonia
or mono- or polyamines, as described, in particular, in EP-A
476,485.
[0113] Additives containing carboxylic acid groups or the alkali
metal or alkaline earth metal salts thereof (d) are preferably
copolymers of C.sub.2-C.sub.40 olefins with maleic anhydride having
a total molecular weight of from 500 to 20,000 whose carboxylic
acid groups have been converted entirely or partially to the alkali
metal or alkaline earth metal salts and the remainder of the
carboxylic acid groups has been caused to react with alcohols or
amines. Such additives are disclosed, in particular, in EP-A
307,815. Said additives mainly serve to prevent valve seat
recession and can be used, as described in WO-A 87/01126, with
advantage combined with conventional fuel detergents such as
poly(iso)butylene amines or polyether amines.
[0114] Additives containing sulfo groups or the alkali metal or
alkaline earth metal salts thereof (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 mainly
serve to prevent valve seat recession and can be used with
advantage combined with conventional fuel detergents such as
poly(iso)butylene amines or polyether amines.
[0115] Additives containing polyoxy-(C.sub.2-C.sub.4 alkylene)
groups (f) are preferably polyethers or polyether amines, which are
obtained by reaction of C.sub.2-C.sub.60 alkanols, C.sub.6-C.sub.30
alkanediols, mono- or di-(C.sub.2-C.sub.30 alkyl)amines,
(C.sub.1-C.sub.30 alkyl)cyclohexanols or (C.sub.1-C.sub.30
alkyl)phenols 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 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 flotation oil characteristics. Typical examples
thereof are tridecanol butoxylates or isotridecanol butoxylates,
isononylphenol butoxylates, polyisobutenol butoxylates and
polyisobutenol propoxylates and the corresponding reaction products
with ammonia.
[0116] Additives containing carboxylate groups (g) are preferably
esters of mono-, di- or tricarboxyllc 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 3,838,918. The mono-, di- or tri-carboxylic acids used can be
aliphatic or aromatic acids, and suitable ester alcohols or ester
polyols are primarily long-chain representatives containing, for
example, from 6 to 24 carbon atoms. Typical representatives of
these esters are adipates, phthalates, isophthalates,
terephthalates and trimellitates of isooctanol, isononanol,
isodecanol and isotridecanol. Such products also have flotation oil
characteristics.
[0117] Additives containing groups derived from succinic anhydride
and containing hydroxyl and/or amino and/or amido and/or imido
groups (h) are preferably corresponding derivatives of
polyisobutenyl succinic anhydride, which are obtained by reaction
of conventional or highly reactive polyisobutylene having a
molecular weight M.sub.n of from 300 to 5000 with maleic anhydride
by thermal treatment or via chlorinated polyisobutylene. Of special
interest in this respect are derivatives with aliphatic polyamines
such as ethylenediamine, diethylenetriamine, triethylenetetramine
or tetrethylenepentamine. Such fuel additives are described, in
particular, in U.S. Pat. No. 4,849,572.
[0118] Additives containing groups (i) produced by Mannich reaction
of substituted phenols with aldehydes and mono- or polyamines are
preferably reaction products of polyisobutylene-substituted phenols
with formaldehyde and mono- or polyamines such as ethylenediamine,
diethylenetriamine, triethylenetetramine, tetrethylenepentamine or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols
can be derived from conventional or highly reactive polyisobutylene
having a molecular weight M.sub.n of from 300 to 5000. Such
"polyisobutylene Mannich bases" are described, in particular, in
EP-A 831,141.
[0119] To provide a more precise definition of the individual fuel
additives mentioned above, the disclosures of the aforementioned
specifications of the prior art are included herein by
reference.
B) Carrier Oils
[0120] Examples of conventional carrier oils are, for example,
mineral carrier oils (base oils) and synthetic carrier oils.
Examples for suitable mineral carrier oils are in particular those
of viscosity class Solvent Neutral (SN) 500 to 2000, as well as
aromatic and paraffinic hydrocarbons and alkoxyalkanols. Examples
for synthetic carrier oils are olefin polymers with M.sub.N=400 to
1800 based on poly-alpha-olefins or poly-internal-olefins,
especially those based on polybutene or on polyisobutene
(hydrogenated or nonhydrogenated); further polyesters,
polyalkoxylates, polyethers, aliphatic polyether amines, and
carboxylic acids of long-chain alkanols. Preferably, synthetic
carrier oils are used. Preferred synthetic carrier oils are alkanol
alkoxylates, in particular alkanol propoxylates and alkanol
butoxylates.
C) Further Additives
[0121] Further conventional components and assistants are corrosion
inhibitors, for example based on ammonium salts of organic
carboxylic acids different from compounds I, which salts tend to
form films, or on heterocyclic aromatics in the case of corrosion
protection of nonferrous metals, antioxidants or stabilizers, for
example based on amines, such as p-phenylenediamine,
dicyclohexylamine or derivatives thereof and on phenols, such as
2,4-di-tert-butylphenol or
3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, dehazers,
demulsiflers, antistatic agents, metallocenes such as ferrocene or
methylcyclopentadienyl manganese tricarbonyl, lubricity additives
(different from compound (I)), such as certain fatty acids,
alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines,
hydroxyacetamides and castor oil, antiknock additives, anti-icing
additives, octane requirement additives, and also colorants
(markers). Sometimes amines are also added for increasing the pH of
the fuel.
[0122] The invention is further related to a fuel gasoline I
composition containing a gasoline as major component and at least
one compound of the formula (I) as defined above and optionally at
least one further additive. Suitable additives are those listed
above.
[0123] The term "gasoline" includes blends of distillate
hydrocarbon fuels with oxygenated compounds such as ethanol, as
well as the distillate fuels themselves.
[0124] Suitable gasolines are e.g. those described in Ullmann's
Encyclopedia of Industrial Chemistry, 5.sup.th edition, 1990,
volume A16, page 719 ff.
[0125] Suitable gasolines are e.g. those having an aromatics
content of not more than 60% by volume, e.g. 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, e.g. not more than 150 ppm by
weight or not more than 10 ppm by weight.
[0126] In a preferred embodiment, the aromatics content of the
gasoline is e.g. from 10 to 50% by volume, e.g. from 30 to 42% by
volume, in particular from 32 to 40% by volume or not more than 35%
by volume.
[0127] In another preferred embodiment, the sulfur content is e.g.
of from 2 to 500 ppm by weight, e.g. of from 5 to 100 or not more
than 10 ppm by weight.
[0128] In another preferred embodiment, the olefin content of the
gasoline can be up to 50% by volume, e.g. from 6 to 21% by volume,
in particular from 7 to 18% by volume.
[0129] In another preferred embodiment, the gasoline has a benzene
content of not more than 5% by volume, e.g. from 0.5 to 1.0% by
volume, in particular from 0.6 to 0.9% by volume.
[0130] In another preferred embodiment, the gasoline has an oxygen
content of not more than 25% by weight, e.g. up to 10% by weight or
from 1.0 to 2.7% by weight, and in particular from 1.2 to 2.0% by
weight.
[0131] Particular preference is given to a gasoline which has an
aromatics content of not more than 38% by volume or preferably not
more than 35% by volume, and at the same time 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.
[0132] The amount of alcohols and ethers contained in the gasoline
may vary over wide ranges. Typical maximum contents are e.g.
methanol 15% by volume, ethanol 65% by volume, isopropanol 20% by
volume, tert-butanol 15% by volume, isobutanol 20% by volume and
ethers containing 5 or more carbon atoms in the molecule 30% by
volume. The summer vapor pressure of the gasoline (at 37.degree.
C.) is usually not more than 70 kPa, in particular not more than 60
kPa.
[0133] The research octane number (RON) of the gasoline is usually
from 75 to 105. A usual range for the corresponding motor octane
number (MON) is from 65 to 95.
[0134] The above characteristics are determined by conventional
methods (DIN EN 228).
[0135] Moreover, the invention is related to an additive
concentrate, comprising at least one compound of the formula (I) as
defined above and at least one diluent and optionally at least one
further additive. Suitable additional additives are those mentioned
above.
[0136] Preferably, the additive concentrate of the invention
contains at least one further additive selected from carrier oils,
detergents, corrosion inhibitors, demulsifiers, conductivity
improvers, odorants, markers, dyes, solvents, anti-valve seat
recession additives and octane requirement additives. More
preferably, the additive concentrate of the invention contains at
least one carrier oil and optionally at least one further additive
selected from detergents, corrosion inhibitors, demulsifiers,
conductivity improvers, odorants, markers, dyes, solvents,
anti-valve seat recession additives and octane requirement
additives. Even more preferably, the additive concentrate of the
invention contains at least one carrier oil, at least one detergent
and/or corrosion inhibitor and optionally at least one further
additive selected from demulsifiers, conductivity improvers,
odorants, markers, dyes, solvents, anti-valve seat recession
additives and octane requirement additives.
[0137] Preferably, the detergent is selected from detergents of the
above group (a), in particular polyisobutene monoamines, and
detergents of the above group (i), in particular polyisobutyl
Mannich bases.
[0138] In the additive concentrate of the invention, the
compound(s) of formula I are preferably present in an amount of
from 0.1 to 95% by weight, more preferably from 1 to 80% by weight,
even more preferably from 5 to 70% by weight, in particular from 10
to 70% by weight, based on the total weight of the concentrate. If
the additive concentrate contains a further additive, the compounds
of formula I are preferably present in an amount of from 0.1 to 80%
by weight, more preferably from 1 to 70% by weight, even more
preferably from 5 to 50% by weight, in particular from 5 to 30% by
weight, based on the total weight of the concentrate.
[0139] Suitable diluents are e.g. aromatic and aliphatic
hydrocarbons, such as benzene, toluene, the xylenes, solvent
naphtha, and alkanols with 3 to 8 carbon atoms, e.g. propanol,
isopropanol, n-butanol, sec-butanol, isobutanol and the like, in
combination with hydrocarbon solvents, and alkoxyalkanols.
Finally, the invention is related to a method for producing a
gasoline composition with improved friction properties, where a
gasoline or a commercial gasoline composition is additized with at
least one compound of the formula (I) as defined above or with the
additive concentrate as defined above.
[0140] The compound(s) of formula (I) and optionally said
additional additives are metered into the gasoline or gasoline
composition, where they become effective. The compounds (I) and
optionally the additional additives can be added to the gasoline or
to gasoline fuel composition individually or as a previously
prepared additive concentrate (additive package).
[0141] The compounds of formula (I) exhibit, in addition to their
good friction modifying characteristics, a good compatibility with
other additives and solvents in the additive concentrates and a
good solubility in the fuel. Moreover, they do not adversely affect
the properties of other additives present in the fuel or in the
additive concentrate. In particular, they do not promote the
formation of water/fuel emulsions, which is a serious problem in
regard of corrosion, filter plugging, accumulation of contaminants
in the engine and engine wear. Furthermore, they exhibit an
additional corrosion protection for metals, especially for
aluminium, magnesium, tin, lead, copper, iron, zinc, chromium,
manganese and silver, and for alloys containing at least one of
these metals.
[0142] The invention is illustrated by, but not restricted to, the
following examples.
EXAMPLES
1. Preparation Examples
1.1 Preparation of Octadecenyl-Substituted Succinic Anhydride
[0143] 126 g of octadec-1-ene and 0.37 g of HQME (hydroquinone
monomethyl ether) were heated to 180.degree. C. and 49 g of maleic
anhydride were added. The reactive mixture was stirred at
200.degree. C. until a product mixture containing 10.2%
octadec-1-ene, 74.6% of the monomaleinated product and 15.1% of the
bismaleinated product was obtained. Unreacted maleic anhydride was
removed under high-vacuum conditions.
1.2 Preparation of Octadecenyl-Substituted Succinic Acid
[0144] 50 g of the product obtained in example 1.1 were stirred in
the presence of 20 g water at 100-130.degree. C. Excessive water
was removed at 70.degree. C. under reduced pressure. The obtained
product had an acid number of 6.2 mmol/g.
1.3 Preparation of Oligohexenyl-Substituted Succinic Acid
[0145] An oligohexene containing 80% trimer of hexene (and 20%
tetramer and higher hexene oligomers; obtained by oligomerization
of 3-hexene according to the procedure described in WO 00/39058),
was reacted with maleic anhydride as described in example 1.1. 6.5
g of the resulting product were dissolved in 100 ml
tetrahydrofurane and hydrolyzed with 1.625 g of KOH at room
temperature. 10 g of a strong acidic ion exchanger were added and
the mixture was stirred for 30 minutes. After filtration, the
solvent was evaporated under reduced pressure to yield a product
having an acid number of 3.8 mmol/g.
1.4 Preparation of Dodecenyl-Substituted Succinic Acid
[0146] 13.3 g of 2-dodecen-1-yl succinic anhydride were reacted as
described in example 1.3 to yield a product having an acid number
of 7.0 mmol/g.
2. Preparation of the Fuel Compositions
[0147] Keropur.RTM. 3458N (commercial product of BASF containing
polyisobutene amine with M.sub.n=1000 and tridecanolpolypropoxylate
(tridecanol 15.times.PO) and also a dimeric fatty acid as corrosion
protection)) was heated to 60.degree. C. To this was added a
compound of formula (I) (additive of table 1 below) and the mixture
was stirred at that temperature for one hour.
3. Application Examples
High Frequency Reciprocating Rig (HFFR)-Test
[0148] For evaluating the lubricity/wear of gasolines, a High
Frequency Reciprocating Rig (HFFR)-test--a standard procedure for
evaluating diesel fuel lubricity--was carried out using a
HFFR-apparatus from PCS instruments, London. The test conditions
(according to CEC F-06-A-96) were modified to suit the use of
gasolines (temperature: 25.degree. C.; load: 720 g). The
applicability of the HFFR-test to gasolines is proved by D.
Margaroni, Industrial Lubrication and Tribology, Vol. 50, No. 3,
May/June 1998, pp. 108-118, and W. D. Ping, S. Korcek, H. Spikes,
SAE Techn. Paper 962010, pp. 51-59 (1996).
[0149] Prior to testing, the gasolines (gasolines according to EN
228) were gently concentrated to 50 vol.-% using the distillation
apparatus MP 628 from Herzog, Lauda-Konigshofen, Germany. The
lubricity of the unadditized concentrated gasoline (control) was
tested according to the above-described HFFR-test and compared with
the lubricity observed when the concentrated gasoline was additized
as shown in table 1. The resulting wear scar diameters are also
listed in table 1. The lower the value of the wear scar diameter,
the better the performance of the additive in the fuel
composition.
TABLE-US-00001 TABLE 1 Wear Scar Diameters in Gasoline Wear Scar
Treat Rate Diameter Example Additive [mg/kg] [.mu.m] 3.1 control --
919 3.2 Keropur 3458 N 500 874 3.3 Keropur 3458 N + product of 500
+ 50 732 example 1.3 3.4 Keropur 3458 N + product of 500 + 100 650
example 1.3 3.5 Keropur 3458 N + product of 500 + 50 827 example
1.4
4. Emulsification Behavior According to DIN 51415
[0150] The test was carried out with 500 mg/kg Keropur 3458 N and
50 mg/kg tetrapropenylsuccinic acid in a gasoline according to EN
228 (RON 95; pH 7). The results are shown in table 2 below.
TABLE-US-00002 TABLE 2 Emulsification minutes rating 1 1B 5 1 30 1
60 1
[0151] As the results show, no emulsion is formed.
* * * * *