Note: Descriptions are shown in the official language in which they were submitted.
0000053884 CA 02497123 2005-02-25
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1
Additive Mixture For Fuel and Lubricants
The present invention relates to additive mixtures which
comprise, as component A, at least one additive having detergent
action and, as component B, at least one partially or completely
neutralized fatty acid. The invention further relates to the use
of these additive mixtures for additizing fuel and lubricant
compositions, and also to motor fuel and lubricant compositions
and concentrates which comprise this additive mixture.
The efforts to reduce damaging emissions in the combustion of
motor fuels, in particular of diesel fuels, have concentrated in
recent times on the reduction of sulfur dioxide emissions and
also the reduction of particle emissions, in particular in diesel
exhaust fumes. To reduce sulfur dioxide emissions, the sulfur
content in gasoline and diesel fuels has been reduced in recent
years in refineries by hydrotreatment, in which the fuel is
treated with hydrogen to reduce sulfur-containing components to
hydrogen sulfide. An undesired secondary effect of this
desulfurization is the destruction of polyaromatic and polar
components in the fuel. Expecially in the case of diesel fuels,
this has adverse effects, since diesel engines are
fuel-lubricated and, as a consequence of the reduction of the
natural lubricity of the fuel, the wear increased, in particular
in the region of the high pressure injection pumps. The wear
problem becomes even more significant when the fuels are used in
a mixture with gas to liquid (GTL) fuels or with renewable fuels
such as bioethanol, since these components have no
lubricity-improving properties at all.
To avoid wear, synthetic lubricity improvers, such as fatty acid
mixtures, their esters, amides or salts, are generally added to
the fuel.
Motor fuels are also additized with detergents which are intended
to reduce carbon deposits caused by the fuel in the region of the
injection nozzles and orifices which, inter alia, in
direct-injection high-performance systems such as common rail,
pump-nozzle or pump-line-nozzle, impair the optimum formation of
a fine fuel mist and thus lead to increased fuel consumption and
emissions.
Additives having detergent action for improving the lubricity of
fuels are described, for example, in WO-A-96/23855. The additive
compositions described there comprise an N-acylated compound
0000053884 CA 02497123 2005-02-25
2
30
which burns ashlessly and a carboxylic acid or a carboxylic ester
and are intended to improve the lubricity.
WO-A-01138463 describes the use of fatty acid salts of
5 alkoxylated oligoamines as lubricity improvers for mineral oil
products.
A disadvantage of the additives and additive mixtures described
in the prior art is that relatively high dosages are required to
10 achieve a lubricity-improving effect.
It is an object of the present invention to provide additive
mixtures which successfully improve the lubricity of fuel and
lubricant compositions even at relatively low dosages.
We have found that this object is achieved in that, surprisingly,
combinations of additives having detergent action and of
partially or completely neutralized fatty acids exhibit a
synergistic effect with regard to the improvement of lubricity
and, at the same time, the detergency of fuel and lubricant
compositions.
The present invention therefore provides an additive mixture
comprising
i) as component A, at least one additive having a detergent
action which has at least one hydrophobic hydrocarbon radical
having a number average molecular weight (Mn) of from 85 to
20000 and at least one polar terminal group, and
ii) as component B, at least one partially or completely
neutralized fatty acid.
Preference is given to selecting the polar terminal group of
35 component A from
(a) mono- or polyamino groups having up to 6 nitrogen atoms where
at least one nitrogen atom has basic properties,
40 (b) nitro groups, optionally in combination with hydroxyl groups,
(c) hydroxyl groups in combination with mono- or polyamino groups
where at least one nitrogen atom has basic properties,
0000053884 CA 02497123 2005-02-25
a ,
3
(d) polyoxy-C2-C4-alkylene groups which are terminated by hydroxyl
groups, mono- or polyamino groups where at least one nitrogen
atom has basic properties, or by carbamate groups,
(e) carboxylic ester groups,
(f) groups formed by Mannich reaction of substituted phenols with
aldehydes and mono- or polyamines and
(g) groups which are derived from carboxylic anhydrides and have
hydroxyl and/or amino and/or amido and/or imido groups.
Additives containing mono- or polyamino groups (a) are preferably
polyalkenemono- or polyalkenepolyamines based on polypropene or
on reactive (i.e. having predominantly terminal double bonds,
usually in the ~- and y-positions) or conventional (i.e. having
predominantly internal double bonds) polybutene or polyisobutene
having an MN of from 300 to 5000. Such additives based on reactive
polyisobutene, which can be prepared from the polyisobutene
(which may contain up to 20~ by weight of n-butene units) by
hydroformylation and reductive amination with ammonia, monoamines
or polyamines, such as dimethylaminopropylamine ethylenediamine,
diethylenetriamine, triethylenetetramine or
tetraethylenepentamine, are disclosed in particular in EP-A
244 616. When polybutene or polyisobutene having predominantly
internal double bonds (usually in the (3 and y positions) are used
as starting materials in the preparation of the additives, the
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 the same as those used above for the
reductive amination of the hydroformylated reactive
polyisobutene. Corresponding additives based on polypropene are
described in particular in WO-A 94124231, which is fully
incorporated herein by way of reference.
Further preferred additives containing monoamino groups (a) are
the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P of
from 5 to 100 with oxides of nitrogen or mixtures of oxides of
nitrogen and oxygen, as described in particular in WO-A 97/03946,
which is fully incorporated herein by way of reference.
Further preferred additives containing monoamino groups (a) are
the compounds obtainable from polyisobutene epoxides by reaction
with amines and subsequent dehydration and reduction of the amino
0000053884 CA 02497123 2005-02-25
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4
alcohols, as described in particular in DE-A 196 20 262 which is
fully incorporated herein by way of reference.
Additives containing vitro groups, optionally in combination with
hydroxyl groups, (b) are preferably reaction products of
polyisobutenes 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, which are fully incorporated herein
by way of reference. These reaction products are generally
mixtures of pure nitropolyisobutanes (e. g.
a,~-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes
(e. g. a-vitro-[3-hydroxypolyisobutane).
Additives containing hydroxyl groups, optionally 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 an MN of
from 300 to 5000, with ammonia or mono- or polyamines, as
described in particular in EP-A 476 485, which is fully
incorporated herein by way of reference.
Additives containing polyoxy-C2- to C4-alkylene groups (d) are
preferably polyethers or polyetheramines which are obtainable by
reaction of C2- to C6o-alkanols, C6- to C3o-alkanediols, mono- or
di-C2-C3o-alkylamines, C1-C3o-alkylcyclohexanols or
C1-C3o-alkylphenols with from 1 to 30 mol of ethylene oxide and/or
propylene oxide and/or butylene oxide per hydroxyl group or amino
group and, in the case of the polyetheramines, by subsequent
reductive amination with ammonia, monoamines or polyamines. Such
products are described in particular in EP-A 310 875, EP-A
356 725, EP-A 700 985 and US-A 4 877 416, which are fully
incorporated herein by way of reference. 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 the corresponding
reaction products with ammonia.
Additives containing carboxylic ester groups (e) are preferably
esters of mono-, di- or tricarboxylic acids with long-chain
alkanols or polyols, in particular those having a minimum
viscosity of 2 mm2 at 100~C, as described in particular in DE-A
38 38 918, which is fully incorporated herein by way of
reference. 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,
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v
for example, 6 to 24 carbon atoms. Typical representatives of the
esters are adipates, phthalates, isophthalates, terephthalates
and trimellitates of isooctanol, of isononanol, of isodecanol and
of isotridecanol. Such products also have carrier oil properties.
5
Additives containing groups produced by conventional Mannich
reaction of phenolic hydroxyl groups with aldehydes and mono- or
polyamines (f) are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and primary
mono- or polyamines, such as ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine. Such polyisobutene Mannich bases are
described in particular in EP-A 831 141, which is fully
incorporated herein by way of reference.
Additives containing groups which are derived from carboxylic
anhydrides and have hydroxyl and/or amino and/or amido and/or
imido groups (g) are preferably corresponding derivatives of
dicarboxylic anhydrides, more preferably of succinic anhydride.
The polar group of component A is more preferably a group which
is derived from carboxylic anhydrides and has hydroxyl and/or
amino and/or amido and/or imido groups (g), in particular having
amido and/or imido groups, i.e. N-acyl groups.
Component A is preferably an acylated nitrogen compound (N-acyl
compound) which burns ashlessly and has a polar group (g).
However, component A may, in addition to the preferred acylated
nitrogen compound (N-acyl compound) which burns ashlessly and has
a polar group (g), also comprise one or more further compounds
which correspond to the combination of hydrophobic hydrocarbon
radicals with the abovementioned polar groups (a) to (f).
The hydrophobic hydrocarbon radical of component A is preferably
a homo- or copolymer radical whose repeating units are derived
from monomers which are selected from propene, n-butene and
isobutene and mixtures thereof.
The homo- or copolymer radical is more preferably a polyisobutene
radical. In particular, the homo- or copolymer radical is a
"reactive" polyisobutene radical which differs from
"low-reactivity" polyisobutenes by the terminal double bond
content. Reactive polyisobutenes differ from low-reactivity
polyisobutenes in that they have not less than 50 mol%,
preferably not less than 60 mol% and more preferably not less
than 80 mol%, of terminal double bonds, based on the total number
t ' 0000053884 CA 02497123 2005-02-25
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of polyisobutene macromolecules. The terminal double bonds may
either be vinyl double bonds [-CH=C(CH3)2] or else vinylidene
double bonds [-CH2-C(=CHZ)-CH3]. Preference is given in particular
to polyisobutenes which have uniform polymer backbones. Those
polyisobutenes in particular which are composed of at least 85%
by weight, preferably at least 90% by weight and more preferably
at least 95% by weight, of isobutene units have a uniform polymer
backbone. Such reactive polyisobutenes preferably have a number
average molecular weight in the range from 200 to 20 000.
Reactive polyisobutenes in particular which have a number average
molecular weight in the range from 300 to 3 000, more preferably
from 400 to 2 500 and most preferably from 500 to 1 500, for
example a number average molecular weight of about 550, about
800, about 1 000 or about 2 300 are suitable for preparing fuel
additives. Reactive polyisobutenes in particular which have a
number average molecular weight in the range from 1000 to 15 000,
more preferably from 1300 to 12500 and most preferably from 2000
to 10 000, for example a number average molecular weight of about
1500, about 2000 or about 2300 are suitable for preparing
lubricant additives. Furthermore, the reactive polyisobutenes
preferably have a polydispersity of less than 3.0, in particular
less than 1.9 and more preferably less than 1.7 or less than 1.5.
Polydispersity is the quotient of the weight average molecular
weight MW divided by the number average molecular weight MN.
Examples of particularly suitable reactive polyisobutenes include
the Glissopal brands from BASF AG, in particular Glissopal 1000
(MN = 1 000) and Glissopal V 33 (MN = 550) and Glissopal 2300 (MN
- 2 300) and their mixtures. Other number average molecular
weights may be attained in the manner known in principle by
mixing polyisobutenes of different number average molecular
weights or by extractive enrichment of polyisobutenes of certain
molecular weight ranges.
Component A is preferably an N-acyl compound which burns
ashlessly and is derived from a polar group (g) which is
substituted by a homo- or copolymer radical. Preferred polar
groups (g) and preferred hydrophobic hydrocarbon radicals are
those mentioned previously. The acyl compound which burns
ashlessly is more preferably an N-acyl compound which is derived
from polyalkenylsuccinic anhydrides and especially from
polyisobutenylsuccinic anhydrides. Of particular interest in this
connection are N-acyl compounds which are obtainable by reacting
the anhydride with aliphatic polyamines, such as ethylenediamine,
diethylenetriamine, triethylenetetramine or
tetraethylenepentamine. Such N-acyl compounds are described in
0000053884 CA 02497123 2005-02-25
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particular in US-A 4 849 572, which is fully incorporated herein
by way of reference.
The polyisobutenylsuccinic anhydride is obtainable, for example,
by reacting conventional or reactive polyisobutene having MN from
300 to 5 000 with malefic anhydride by thermal routes or via the
chlorinated polyisobutene.
The acylated nitrogen compound which burns ashlessly and has a
polar group (g) is obtainable, for example, by reacting a
carboxylic acid substituted by a hydrophobic hydrocarbon radical
or a carboxylic acid derivative substituted by a hydrophobic
hydrocarbon radical with an amine which has at least one NH or NHz
group. Preference is given to reacting a carboxylic anhydride.
As detailed hereinabove, the carboxylic acid or carboxylic acid
derivative is more preferably a dicarboxylic acid or a
dicarboxylic acid derivative, preferably a dicarboxylic
anhydride, in particular a succinic acid or succinic acid
derivative, preferably a succinic anhydride. Preference is given
to polyalkenylsuccinic acids or polyalkenylsuccinic acid
derivatives, preferably polyalkenylsuccinic anhydrides,
especially polyisobutenylsuccinic anhydride.
The reaction of dicarboxylic acids or their derivatives,
especially dicarboxylic anhydrides, with amines may result in
product mixtures which comprise dicarboxylic monoamides,
dicarboxylic diamides, ammonium salts of dicarboxylic monoamides,
dicarboxylic monoamide monoesters, amidines and also dicarboxylic
mono- and diimides. Useful components A are both the individual
acylation products mentioned and their mixtures. However,
preference is given to dicarboxylic imides, in particular
dicarboxylic monoimides.
For the reaction with the carboxylic acid or carboxylic acid
derivative, useful amines are both monoamines, i.e. amines having
only one amino function in the molecule, and polyamines, i.e.
those having at least two amino functions in the molecule.
Useful monoamines are both primary and secondary aliphatic amines
having from 3 to 10 carbon atoms, such as propylamine,
butylamine, pentylamine, hexylamine, octylamine, diethylamine,
dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine,
N-methylcyclohexylamine, N-ethylcyclohexylamine, piperidine,
piperazine and morpholine. Mixtures of monoamines are also
suitable, in particular amine mixtures obtainable on the
industrial scale, such as fatty amines, as described, for
0000053$84 CA 02497123 2005-02-25
example, in Ullmanns Encyclopedia of Industrial Chemistry, 6th
edition, 2000 electronic release, chapter "Amines, aliphatic",
which is fully incorporated herein by way of reference.
5 However, preference is given to using polyamines.
Examples of useful polyamines include those of the formula NR1R2R3
where at least one of the R1, RZ or R3 radicals is a radical of
the following formulae II, III or IV
~-(-CR4R5 ) x-NR6 j-y ( CR~R$ ) z-NR9R1 ° ( II )
f-(-CR4R5 ) x -O'~Y ( CR~RB ) z-NR9R1° ( I I I ) or
15 ~-f-CR4R5 ) x-NR6-~x ( CR~RB ) z-ORi l ( IV )
where
R4, R5, R6, R7, R8 and R11 are each independently H or C1-C6-alkyl,
R9 and R1° are each independently H, C1-C6-alkyl or
C1-C6-hydroxyalkyl,
x and z are each independently a number from 1 to 8 and
y is a number from 0 to 8.
R4, R5, R6, R7, R8 and R11 are preferably each H or methyl.
Those R1, R2 and R3 radicals which are not a radical of the
formula II, III or IV are preferably H, C1-C6-alkyl,
C1-C6-hydroxyalkyl or C3-C~-cycloalkyl, although at least one of
the R1, RZ and R3 radicals has to be H.
In the above definition of the R1, R2, R3, R4, R5, R6, R7, R8 and
Rll radicals, C1-C6-alkyl is in particular methyl, ethyl, propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or
hexyl.
C1-C6-Hydroxyalkyl is in particular the aforementioned C1-C6-alkyl
radicals substituted by a hydroxyl group.
C3-Cs-Cycloalkyl is in particular cyclopropyl, cyclopentyl,
methylcyclopentyl, cyclohexyl, methylcyclohexyl and cyclooctyl.
0000053884 CA 02497123 2005-02-25
9
More preferably, R1 and R2 are H and R3 is a radical of the
formula I where R4, R5, R6, R7, R8 and R1~ are each H.
Examples of useful polyamines include ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, propylenediamine, dipropylenetriamine,
tripropylenetetramine, tetrapropylenepentamine,
pentapropylenehexamine, butylenediamine, dibutylenetriamine,
tributylenetetramine, tetrabutylenepentamine,
pentabutylenehexamine, N,N-dimethylmethylenediamine,
N,N-diethylmethylenediamine, N,N-dipropylmethylenediamine,
N,N-dimethylethylene-1,2-diamine,
N,N-diethylethylene-1,2-diamine,
N,N-dipropylethylene-1,2-diamine,
N,N-dimethylpropylene-1,3-diamine,
N,N-diethylpropylene-1,3-diamine,
N,N-diprogylpropylene-1,3-diamine,
N,N-dimethylbutylene-1,4-diamine,
N,N-diethylbutylene-1,4-diamine,
N,N-dipropylbutylene-1,4-diamine,
N,N-dimethylpentylene-1,5-diamine,
N,N-diethylpentylene-1,5-diamine,
N,N-dipropylpentylene-1,5-diamine,
N,N-dimethylhexylene-1,6-diamine,
N,N-diethylhexylene-1,6-diamine,
N,N-dipropylhexylene-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-diethylamino)propyl)amine,
bis[3-(N,N-dipropylamino)propyl)amine,
bis[4-(N,N-dimethyl-amino)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-diethylamino)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", 2nd edition, Volume 7, pages 22 to 37, Interscience
Publishers, New York (1965), chapter "Ethyleneamines".
0000053884 CA 02497123 2005-02-25
Processes for preparing the abovementioned N-aryl compounds are
known to those skilled in the art. A particularly useful process
for preparing polyalkenylsuccinimides is described in the German
patent application DE-A-10123553.4, which is fully incorporated
5 herein by way of reference. In this process, a
polyalkenylsuccinic anhydride is reacted first with an alcohol or
a phenol and then with an amine. Alternatively, the
polyalkenylsuccinic anhydride is reacted with the amine in the
presence of an alcohol or a phenol.
Alcohols suitable for preparing polyalkenylsuccinic imides are
preferably monohydric; however, polyhydric alcohols are also
suitable.
Preference is giving to using monohydric alcohols having from 1
to 16 carbon atoms, such as methanol, ethanol, propanol,
isopropanol, butanol, sec-butanol, isobutanol, tert-butanol,
2-hydroxymethylfuran, amyl alcohol, isoamyl alcohol,
vinylcarbinol, cyclohexanol, n-hexanol, 6-capryl alcohol,
2-ethylhexanol, n-decanol, lauryl alcohol, isooctyl alcohol and
their mixtures. Preferred alcohols are those having from 6 to 16
carbon atoms. Particular preference is given to 2-ethylhexanol.
Useful phenols include phenol, naphthol, (o,p)-alkylphenols and
salicylic acid.
Processes for preparing polyalkenyl-substituted carboxylic acids
and their derivatives are well known. For instance, the German
patent application DE-A-10123553.4 describes the preparation of a
polyolefin-substituted carboxylic acid or a derivative thereof by
the reaction of a polyalkene with a monounsaturated acid or its
derivative, in which the polyalkylene adds in an ene reaction to
the double bond of the acid component.
Component B is preferably a fatty acid partly or completely
neutralized by amines.
Component B more preferably comprises at least one fatty acid
salt of the formula I
H-(OA)xl~~ O
NH Z - NH ( AO ) X3-H ( R-C00~) m+1 ( I )
H-(OA)xz~
(AO)X4-H m
00000538$4 CA 02497123 2005-02-25
11
where
R is C7-C23-alkyl or a mono- or polyunsaturated C7-C23-alkenyl,
each of which may optionally be substituted by one or more
hydroxyl groups;
A is C2-Ce-alkylene;
Z is C1-C8-alkylene, C3-C8-cycloalkylene, C6-C12-arylene or
C7-CZO-arylalkylene;
m is a number from 0 to 5; and
xl, x2, x3 and x4 are each independently a number from 0 to 24,
where at least one x is not 0,
and optionally at least one further fatty acid RCOOH, where R is
as defined above.
Such fatty acid salts are described, for example, in WO 01/38463
which is fully incorporated herein by way of reference.
The relatively long-chain R radical occurring in the carboxylate
anion RCOO- or in the fatty acid RCOOH is, for example, a branched
or preferably linear C7- to C23-, preferably C11- to CZ1-, in
particular C15- to C19-alkyl group which may additionally bear
hydroxyl groups. Examples of parent carboxylic acids include
octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic
acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic
acid, isotridecanoic acid, tetradecanoic acid (myristic acid),
hexadecanoic acid (palmitic acid), octadecanoic acid (stearic
acid) and eicosanoic acid. The acids mentioned may be of natural
or synthetic origin. The carboxylate anions may also be based on
mixtures of the acids mentioned.
However, the relatively long-chain R radical occurring in the
carboxylate anion RC00- or in the fatty acid RCOOH is preferably a
mono- or polyunsaturated C7 to Cz3 radical, especially a mono- or
polyunsaturated C11- to Czl-, in particular C15- to C19-alkenyl
group which may additionally bear hydroxyl groups. These
unsaturated radicals are preferably linear. In the case of
polyunsaturated alkenyl groups, these preferably contain two or
three double bonds. Examples of parent carboxylic acids include
elaidic acid, ricinoleic acid, linoleic acid and linolenic acid.
Particularly good results are achieved using oleic acid. The
carboxylate anions may also be based on mixtures of such
unsaturated carboxylic acids with each other and also with the
0000053884 CA 02497123 2005-02-25
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12
abovementioned saturated carboxylic acids. Examples of such
mixtures include tall oil, tall oil fatty acid and rapeseed oil
fatty acid. The unsaturated carboxylic acids mentioned and the
mixtures mentioned are generally of natural origin.
The alkylene group A in compounds of the formula I is preferably
derived from appropriate alkylene oxides such as ethylene oxide,
1,2-propylene oxide, 1,2-butylene oxide and cis- or
trans-2,3-butylene oxide. However, it may also be 1,3-propylene,
1,4-butylene, 1,6-hexylene or 1,8-octylene, A may likewise be a
mixture of different groups mentioned. A is more preferably
ethylene, 1,2-propylene or 1,2-butylene groups.
The variable Z is in particular C1- to C4-alkylene groups such as
methylene, 1,2-propylene, 1,2-butylene, 1,3-butylene or
2,3-butylene, C5- to C6-cycloalkylene groups such as
1,3-cyclopentylidene or 1,3- or 1,4-cyclohexylidene or C6- to
C$-arylene or -arylalkylene groups such as 1,3- or 1,4-phenylene,
2-methyl-1,4-phenylene or 1,3- or 1,4-bismethylenephenylene.
However, the variable Z is preferably a polymethylene group of
the formula -(CHZjn- where n = 2 to 8, in particular where n = 2
to 6, i.e, in particular 1,2-ethylene, 1,3-propylene,
1,4-butylene, 1,5-pentylene and 1,6-hexylene, but in addition
also 1,7-heptylene and 1,8-octylene.
When the variable m is 0, the tatty acid salts used as cationic
components in accordance with the invention are generally based,
depending on the sum (E) of all variables xl, xz and x3, on
mixtures of mono-, di- and/or trialkanolamines or pure
trialkanolamines. Examples of such alkanolamines include
monoethanolamine, diethanolamine, triethanolamine,
monoisopropanolamine, diisopropanolamine, triisopropanolamine and
also the corresponding mixtures. Within this group, the oleic
acid salt of triethanolamine [(xl+x2+x3) = 3; A = ethylene] is of
particular interest.
However, the variable m is preferably the number 1 or 2. When m =
1, the parent molecules are completely and/or partially
alkoxylated alkylenediamines such as 1,2-ethylenediamine,
1,3-propylenediamine or 1,4-butylenediamine. When m = 2, the
parent molecules are usually completely and/or partially
alkoxylated dialkylenetriamines such as di(1,2-ethylene)triamine,
di(1,3-propylene)triamine or di(1,4-butylene)triamine. Within
this group, the bis-oleic acid salts of
N,N,N',N'-tetrakis-(2'-hydroxyethyl)-1,2-ethylenediamine (Ex = 4)
and N,N,N',N'-tetrakis-(2'-hydroxypropyl)-1,2-ethylenediamine (Ex
0000053884 CA 02497123 2005-02-25
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13
- 4) and also the tris-oleic acid salts of
di(1,2-ethylene)triamine reacted with from 4 to 5 mol of ethylene
oxide or 1,2-propylene oxide are of particular interest.
5 However, it is also possible for the amine component on which the
fatty acid salts used in accordance with the invention are based
to be higher homologs of the alkylenediamine and
dialkylenetriamines mentioned, for example triethylenetetramine
(m = 3), tetraethylenepentamine (m = 4) or pentaethylenehexamine
10 (m = 5).
In a preferred embodiment, the number x, i.e. the sum of xl, x2,
x3 and x4 (Ex), of alkylene oxide units (OA) introduced per amine
molecule depends on the number of N-H bonds in the parent amine
15 and may correspond to the number of N-H bonds (Ex = m+3).
However, it is also possible for more or fewer OA units to be
incorporated. In the case of greater than stoichiometric
incorporation, a preferred upper limit is a triple alkoxylation
per N-H bond [300% of (m+3)] with regard to the properties of the
20 resulting fatty acid salts. In the case of less than
stoichiometric incorporation, a corresponding preferred lower
limit is on average 50% of the alkoxylation [50% of (m+3)]; this
results in mixes of species having different degrees of
alkoxylation.
In a particularly preferred embodiment, the sum (E) of all x
variables has a value of from 75% to 125% of (m+3).
The fatty acid salts of the general formula I can typically be
prepared easily by alkoxylating the parent amine by customary
methods and subsequently neutralizing with the fatty acids of the
formula RCOOH.
When C2- to C4-alkylene oxides are used, the alkoxylation for the
introduction of the first alkylene oxide unit into the N-H bond
is advantageously carried out in the presence of small amounts of
water (usually from 0.5 to 5% by weight, based on the amount of
amine used) without a catalyst at temperatures of from 80 to
140°C, and, for the introduction of further alkylene oxide units,
with the exclusion of water in the presence of basic catalysts
such as alkali metal hydroxides, e.g. sodium hydroxide or
potassium hydroxide, at temperatures of from 100 to 150°C.
The alkoxylated amine obtained in this way is generally
neutralized by heating with the appropriate stoichiometric amount
or a small stoichiometric deficiency (i.e. from 90 to 100%, in
particular from 95 to 100%, of theory) of fatty acid to
0000053884 CA 02497123 2005-02-25
14
temperatures of from 30 to 100°C, in particular from 40 to 80°C,
for a period of from 15 minutes to 10 hours, in particular from
30 minutes to 5 hours. The neutralization reaction should be
conducted in such a way that no carboxylic ester fractions form
in the product. In many cases, both the alkoxylated amine and the
fatty acid may be used as liquids which makes the reaction to
give the corresponding fatty acid salts particularly simple. The
sequence of addition of alkoxylated amine and fatty acid is
uncritical, i.e. it is possible to either initially charge the
alkoxylated amine and add the fatty acid or initially charge the
fatty acid and add the alkoxylated amine.
However, it is also possible in principle to add the alkoxylated
amine and the fatty acid as individual components to the additive
concentrates or mineral oil products and allow the salt formation
to take place there.
The molar ratio of component A to component B in the additive
mixture is preferably from 1:10 to 10:1, more preferably from 1:6
to 6:1 and in particular from 1:4 to 4:1.
The present invention further provides the use of the additive
mixture described above for additizing fuel and lubricant
compositions.
Useful fuels are gasoline fuels and middle distillates, such as
diesel fuel, heating oil or kerosene, and preference is given to
diesel fuel.
The diesel fuels are, for example, crude oil raffinates which
typically have a boiling range of from 100 to 400°C. These are
usually distillates having a 95$ point of up to 360°C or even
higher. However, these may also be "ultra low sulfur diesel" or
"city diesel", characterized by a maximum 95% point of, for
example, 345°C and a maximum sulfur content of 0.005 by weight,
or by a 95$ point of, far example, 285°C and a maximum sulfur
content of 0.001$ by weight. In addition to the diesel fuels
obtained by refining, those obtainable by coal gasification or
gas liquefaction ("gas to liquid" (GTL) fuels) are also suitable.
Mixtures of the aforementioned diesel fuels with renewable fuels,
such as biodiesel or bioethanol, are also suitable.
Particular preference is given to using the additive mixture
according to the invention for additizing diesel fuels having a
low sulfur content, i.e. having a sulfur content of less than
0.05 by weight, preferably of less than 0.02 by weight, in
0000053884 CA 02497123 2005-02-25
1S
particular of less than 0.005% by weight and especially of less
than 0.001% by weight, of sulfur.
Particular preference is given to using the additive mixture
according to the invention for reducing carbon deposits caused by
burning in the region of the injection system of diesel engines
with and without direct fuel injection, preferably of diesel
engines having direct fuel injection.
Preference is also given to using the additive mixture according
to the invention for reducing the corrosive action of a fuel.
The present invention further provides a fuel composition
comprising a majority of a hydrocarbon fuel and an effective
amount of the additive mixture according to the invention and
optionally at least one further additive. With regard to the
preferred fuels, reference is made to the above remarks.
The additive mixture according to the invention is preferably
present in the fuel in an amount of from 1 to 1000 ppm by weight,
more preferably from 10 to 500 ppm by weight and in particular
from 50 to 200 ppm by weight, based on the total amount of
additivized fuel.
The present invention further provides a lubricant composition
comprising an effective amount of an additive mixture according
to the invention, a lubricant, and also optionally at least one
further additive.
The invention further provides an additive concentrate comprising
the additive mixture according to the invention, at least one
solvent or diluent, and also optionally at least one further
additive.
Examples of useful diluents include the fractions obtained in
crude oil processing, such as kerosene, naphtha or brightstock.
Furthermore, aromatic and aliphatic hydrocarbons and
alkoxyalkanols are suitable. In the case of middle distillates,
in particular in the case of diesel fuels, preferably used
diluents are naphtha, kerosene, diesel fuels, aromatic
hydrocarbons such as Solvent Naphtha heavy, Solvesso° or Shellsol~
and also mixtures of these solvents and diluents.
The additive mixture according to the invention is preferably
present in the concentrates in an amount of from 0.1 to 80% by
weight, more preferably from 1 to 70% by weight and in particular
0000053884 CA 02497123 2005-02-25
16
from 20 to 60% by weight, based on the total weight of the
concentrate.
Useful additives which may be present in the fuel or concentrate
according to the invention in addition to the additive mixtures
according to the invention, in particular for diesel fuels,
include detergents, corrosion inhibitors, dehazers, demulsifiers,
antifoams, antioxidants, metal deactivators, multifunctional
stabilizers, cetane number improvers, combustion improvers, dyes,
markers, solubilizers, antistats, other customary lubricity
improvers, additives which improve the cold properties, such as
flow improvers ("MDFI"), paraffin dispersants ("WASA") and the
combination of the two last-mentioned additives ("WAFI").
Examples of the customary lubricity improvers include carboxylic
acids, especially fatty acids, their esters, especially with
polyols, mixtures of these acids and esters, N-acyl compounds
which burn ashlessly, such as polyalkenylsuccinamides, mixtures
of the abovementioned acids and/or esters with these N-acyl
compounds, as described, for example, in WO 96/23855,
bis(hydroxyalkyl)fatty amines or hydroxyacetamides.
Examples of useful flow improvers include oil-soluble, polar
nitrogen compounds such as ammonium salts and/or amides of mono-
or polycarboxylic acids or sulfonic acids and their mixtures with
copolymers of ethylene and unsaturated carboxylic esters and
optionally comb polymers, as described in WO 95/33805.
The synergistically effective combination of components A and B
in the additive mixture according to the invention leads to a
distinct improvement in the lubricity of fuels additivized by it
and to a distinct reduction in the corrosivity of fuels and
carbonization of jets in comparison to prior art additives.
The examples which follow illustrate the invention.
Examples
The experiments described hereinbelow were carried out using the
following fuels:
diesel fuel according to DIN EN 590 having a sulfur content
of 48 ppm: diesel I
- diesel fuel according to DIN EN 590 having a sulfur content
of 15 ppm (ULSD): diesel II
- diesel fuel according to DIN EN 590 having a sulfur content
of 4 ppm (MK1): diesel III
0000053884 CA 02497123 2005-02-25
t
17
- blend of 5% of biodiesel in 95% of diesel I: blend I
- blend of 8% of ethanol in 91% of diesel I (1% of stabilizer
package): blend II
- gas to liquid fuel: GTL
- blend of 20% of GTL in 80% of diesel I: blend III
1. Synthesis of the components of the additive mixture
1.1 Synthesis of a polyisobutenesuccinimide (detergent I)
In a 1 1 three-neck flask, 630 g of polyisobutenylsuccinic
anhydride (molecular weight of polyisobutene: 1000) (hydrolysis
number 95) were mixed with from 0.2 to 2 mol of 2-ethylhexanol
and heated to 80 to 160°C within 20 minutes. 105 g (0.55 mol) of
tetraethylenepentamine were added. The mixture was stirred at
from 150 to 180°C for from 90 to 180 minutes. The alcohol was then
removed under reduced pressure.
1.2 Synthesis of a lubricity improver (Iubricity I)
58.4 g (0.2 mol) of
N,N,N',N'-tetrakis-(2'-hydroxypropyl)-1,2-ethylenediamine
(obtained from 1,2-ethylenediamine and 4 mol of propylene oxide
in the presence of 3% by weight of water, based on the amount of
amine used) were heated to 60-80°C and admixed with 110.4 g
(0.4 mol) of oleic acid with stirring within two hours. The pH
did not fall below ?. Stirring was continued for a further two
hours. The product obtained had an N-titer of 2.39 mmol/g.
2. Engine experiments
In addition to the combinations according to the invention of
detergent I and lubricity I, detergents customary on the market
which are based on polyisobutenesuccinimide and referred to as
detergent II and lubricity improvers customary on the market
which are based on acid and referred to as lubricity II or based
on ester and referred to as lubricity III were used, and their
performance was compared with the combinations according to the
invention of detergent I and lubricity I.
2.1 Carbonization of jets in Peugeot XUD 9 according to
CEC-F23-A01
The flow restriction at a 0.1 mm needle stroke of the
abovementioned unadditized base fuels and fuel blends was
determined in a Peugeot XUD 9 test engine using the current 10 h
0000053884 CA 02497123 2005-02-25
1$
test procedure according to CEC-F23-A01 and compared with the
carbonization of the jets observed when the additized fuels and
fuel blends were used.
The additized fuels and blends were obtained by adding the
abovementioned combinations of 80 mg/kg of detergent I-II and
120 mg/kg of the lubricity improvers lubricity I-III in each
case.
The following results were obtained:
Fuel Detergent Lubricity Flow Changes
improver restriction **
at a 0.1 mm
needle stroke
($j
Diesel I 0 0 91.6
Diesel II 0 0 91.3
Diesel III 0 0 90.5
Blend I 0 0 91.6
Blend II 0 0 90.0
GTL 0 0 89.9
Blend III 0 0 90.3
Diesel I Detergent 0 64.7
I
Diesel II Detergent 0 68.2
I
Diesel III Detergent 0 69.4
I
Blend I Detergent 0 74.5
1
Blend II Detergent 0 72.3
I
GTL Detergent 0 71.4
I
Blend III Detergent 0 68.9
I
Diesel I Detergent Lubricity I 57.6 0 = 7.1
I
Diesel II Detergent Lubricity I 62.7 ~ = 5.5
I
Diesel III Detergent Luhricity I 60.6 0 = 8.8
I
Blend I Detergent Lubricity I 68.0 D = 6.5
I
Blend II Detergent Lubricity I 64.7 0 = 7.6
I
GTL Detergent Lubricity I 65.1 D = 6.3
I
Blend III Detergent Lubricity I 62.3 0 = 6.6
I
Diesel I Detergent 0 70.8
II
Diesel II Detergent 0 73.9
II
Diesel I Detergent Lubricity II 71.2 0 = -0.4
II
Diesel II Detergent Lubricity 11 75.0 ~ _ -1.1
II
Diesel I Detergent Lubricity III 70.8 D = 0.0
II
Diesel II Detergent Lubricity III 73.7 0 = 0.2
II~
** Differences to the flow restriction measured without lubricity
improver
0000053884 CA 02497123 2005-02-25
19
Compared to the test results obtained with detergent I alone, the
combinations according to the invention of detergent I and
labricity I showed a performance improved by 6-9%. Other
combinations resulted in no significant changes being observed.
2.2 Corrosion tests according to ASTM D 665 A/B
The corrosion behavior of the abovementioned unadditized base
fuels and fuel blends was tested in steel finger tests according
to ASTM D 665 A in distilled water and also ASTM D 665 B in
synthetic salt water and compared with the corrosion behavior
observed when the additized fuels and fuel blends were used.
The additized fuels and blends were obtained by adding the
abovementioned combinations of 80 mg/kg of detergent I-II and
120 mg/kg of the lubricity improvers Lubricity I-III in each
case.
The test results were evaluated according to NACE TM-O1-72 as
fol lows
A ~ 100%rust-free
B++ ~ 0.1%or less the entire surface rusted
of
B+ ~ 0.1 - 5% of entire surface rusted
the
H ~ 5 25% of entire surface rusted
- the
C ~ 25 50% of entire surface rusted
- the
D ~ 50 75% of entire surface rusted
- the
E ~ 75 100% of e entire surface rusted
- th
The following results were obtained:
Fuel Detergent Lubricity Test Corrosion
improver according behavior
to ASTM according
D to NACE
TM-O1-72**
Diesel 1 0 0 665 A C
Diesel II 0 0 665 A B
Diesel III 0 0 665 A B+
Blend I 0 0 665 A C
Blend II 0 0 665 A D
CTL 0 0 665 A C
Blend III 0 0 665 A C
Diesel I Detergent 0 665 A B+
I
Diesel II Detergent 0 665 A B++
I
Diesel III Detergent 0 665 A A
I
Blend I Detergent 0 ~ 665 A B+
1 ~
5
0000053884 CA 02497123 2005-02-25
t '
Fuel Detergen+. Lubricity Test Corrosion
improver according behavior
to ASTM according
D to NACE
TM-Ol-72**
Blend II Detergent 0 665 A B
I
GTL Detergent 0 665 A B+
1
Blend III Detergent 0 665 A B+
I
Diesel I Detergent Lubricity I 665 A A
I
10 Diesel II Detergent Lubricity I 665 A A
I
Diesel III Detergent Lubricity I 665 A A
I
Blend I Detergent Lubricity I 665 A A
1
Blend II Detergent Lubricity I 665 A A
I
GTL Detergent Lubricity I 665 A A
I
15 Blend III Detergent Lubricity I 665 A A
I
Diesel I Detergent 0 665 A C
II
Diesel II Detergent 0 665 A B+
II
Diesel I Detergent Lubricity II 665 A B
II
Diesel II Detergent Lubricity II 665 A B+
II
20 Diesel I Detergent Lubricity III 665 A B++
II
Diesel II Detergent Lubricity III 665 A B+
II
Diesel I 0 0 665 B E
Diesel II 0 0 665 B E
Diesel I Detergent 0 665 B C
I
Diesel II Detergent 0 665 B B
I
Diesel I Detergent Lubricity I 665 B B++
I
Diesel II Detergent r Lubricity 665 B ~ A
I I I
Compared to the test results obtained with detergent I alone, the
combinations according to the invention of detergent I and
lubricity I again showed a distinctly improved performance.
Smaller improvements were observed with the other combinations
tested.
2.3 Determination of lubricity according to HFRR
The lubricity of the unadditized base fuels and fuel blends was
tested in HFRR tests according to ASTM D 6079-99, and compared
with the lubricity observed when the additized fuels and fuel
blends were used.
The additized fuels and blends were obtained by adding the
abovementioned combinations of 80 mg/kg of detergent I and
120 mg/kg of lubricity improver Iubricity I in each case. The
y,JSl.4 [E.tm] which represents the size of the wear patch determined
in each case is shown in the table which follows.
0000053884 CA 02497123 2005-02-25
.~ r
21
The following results were obtained:
Fuel Detergent Lubricity WS1.4 Relative
s improver [Wn] improve-
went [Eunl
**
Diesel I 0 0 633
Diesel rI 0 0 590
Diesel rrr 0 0 611
Blend I 0 0 251
Blend II 0 0 669
GTL 0 0 650
Blend III 0 0 663
Diesel I 0 Lubricity I 389
Diesel II 0 Lubricity I 440
Diesel III 0 Lubricity I 470
Blend I 0 Lubricity I 268
Blend rI 0 Lubricity I 520
GTL 0 Lubricity I 420
Blend IIr 0 Lubricity I 403
Diesel I Detergent Lubricity I 368 D = 21
I
Diesel rr Detergent Lubricity I 427 0 =13
I
Diesel Iii Detergent Lubricity I 445 0 = 25
I
Blend I Detergent Lubricity I 252 ~ =16
I
Blend II Detergent Lubricity I 499 0 = 21
I
GTL Detergent Lubricity I 415 0 = 5
I
Blend III Detergent Lubricity I ~ 387 0 =16
~ I ~
** Differences to WS1.4 values in [dun] measured without detergent
Compared to the test results obtained using lubricity I alone,
the combinations according to the invention of detergent I and
Zubricity I showed a performance improved by 5-25 Vim.
40
