U.S. patent application number 14/032889 was filed with the patent office on 2014-01-23 for use of the reaction product formed from a hydrocarbyl-substituted dicarboxylic acid and a nitrogen compound to reduce fuel consumption.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Harald BOEHNKE, Markus HANSCH, Hannah Marie KOENIG, Ludwig VOELKEL, Marc WALTER.
Application Number | 20140020285 14/032889 |
Document ID | / |
Family ID | 46160882 |
Filed Date | 2014-01-23 |
United States Patent
Application |
20140020285 |
Kind Code |
A1 |
VOELKEL; Ludwig ; et
al. |
January 23, 2014 |
USE OF THE REACTION PRODUCT FORMED FROM A HYDROCARBYL-SUBSTITUTED
DICARBOXYLIC ACID AND A NITROGEN COMPOUND TO REDUCE FUEL
CONSUMPTION
Abstract
The use of the reaction product formed from a
hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and
a nitrogen compound I or a salt thereof ##STR00001## as an additive
in a fuel for reducing fuel consumption in gasoline engines.
Inventors: |
VOELKEL; Ludwig;
(Limburgerhof, DE) ; WALTER; Marc; (Frankenthal,
DE) ; BOEHNKE; Harald; (Mannheim, DE) ;
KOENIG; Hannah Marie; (Mannheim, DE) ; HANSCH;
Markus; (Speyer, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
46160882 |
Appl. No.: |
14/032889 |
Filed: |
September 20, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13307392 |
Nov 30, 2011 |
|
|
|
14032889 |
|
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|
|
61418889 |
Dec 2, 2010 |
|
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Current U.S.
Class: |
44/343 ;
44/347 |
Current CPC
Class: |
C10L 2230/22 20130101;
C10L 1/224 20130101; C10L 1/231 20130101; C10L 1/188 20130101; C10L
1/2387 20130101; C10L 1/226 20130101; C10L 1/221 20130101; C10L
2270/023 20130101; C10L 2200/0209 20130101; C10L 2230/086 20130101;
C10L 10/18 20130101; C10L 1/232 20130101; C10L 2200/0415 20130101;
C10L 10/00 20130101; C10L 2300/20 20130101; C10L 2200/0213
20130101; C10L 1/143 20130101; C10L 1/2437 20130101; C10L 1/1966
20130101; C10L 2200/0423 20130101; C10L 1/2383 20130101; C10L
1/1985 20130101; C10L 1/1616 20130101; C10L 1/19 20130101; C10L
1/238 20130101; C10L 1/1824 20130101 |
Class at
Publication: |
44/343 ;
44/347 |
International
Class: |
C10L 1/232 20060101
C10L001/232 |
Claims
1. A process for reducing fuel consumption in a spark-ignition or
self-igniting internal combustion engine employing a gasoline fuel
comprising adding an effective amount for reducing fuel consumption
of a reaction product formed from (a) a hydrocarbyl-substituted
dicarboxylic acid whose hydrocarbyl radical has 8 to 250 carbon
atoms, or the anhydride thereof, and (b) a nitrogen compound of the
general formula (I): ##STR00005## or a salt of the nitrogen
compound (I), wherein R.sup.1 and R.sup.2 each independently
represent hydrogen or a C1- to C20-hydrocarbyl radical.
2. The process according to claim 1, wherein the
hydrocarbyl-substituted dicarboxylic acid (a) is based on succinic
acid or the anhydride thereof.
3. The process according to claim 1, wherein the hydrocarbyl
substituent (a) is a linear or branched C8- to C40-alkyl or
-alkenyl radical or a polyisobutenyl radical having 24 to 250
carbon atoms.
4. The process according to claim 1, wherein the nitrogen compound
(b) is unsubstituted aminoguanidine hydrogencarbonate.
5. The process according to claim 1, wherein the gasoline fuel
additionally comprises at least one additional additive which is
different from the reaction product and acts as a detergent.
6. The process according to claim 5, wherein the additional
additive is amphiphilic and has at least one hydrophobic
hydrocarbyl radical having a number-average molecular weight of 85
to 20,000, and at least one polar moiety.
7. The process according to claim 6, wherein the additional
additive comprises at least one group selected from the group
consisting of: (Da) a mono- or polyamino group comprising up to 6
nitrogen atoms, at least one nitrogen atom of which having basic
properties; (Db) a nitro group; (Dc) a hydroxyl group in
combination with a mono- or polyamino group, at least one nitrogen
atom of which having basic properties; (Dd) a carboxyl group or its
alkali metal or alkaline earth metal salt; (De) a sulfonic acid
group or its alkali metal or alkaline earth metal salt; (Df) a
polyoxy-C2-C4-alkylene group terminated by at least one hydroxyl
group, mono- or polyamino group, at least one nitrogen atom having
basic properties, or by at least one carbamate group; (Dg) a
carboxylic ester group; (Dh) a group derived from succinic
anhydride and comprising at least one of a hydroxyl group, an amino
group, an amido group, and an imido group; and (Di) a group
obtained by Mannich reaction of at least one substituted phenol
with at least one aldehyde and at least one mono- or polyamine.
8. The process according to claim 5, wherein the gasoline fuel
additionally comprises, in a minor amount, at least one carrier
oil.
9. The process according to claim 1, wherein the gasoline fuel
additionally comprises, in a minor amount, at least one corrosion
inhibitor.
10. The process according to claim 1, wherein the reaction product
is present in an amount of 10 to 5000 ppm by weight of the gasoline
fuel.
11. The process according to claim 1, wherein reaction product is
present in an amount of 20 to 2000 ppm by weight of the gasoline
fuel.
12. The process according to claim 1, wherein reaction product is
present in an amount of 30 to 1000 ppm by weight of the gasoline
fuel.
13. The process according to claim 1, wherein reaction product is
present in an amount of 40 to 500 ppm by weight of the gasoline
fuel.
14. The process according to claim 1, wherein reaction product is
present in an amount of 50 to 300 ppm by weight of the gasoline
fuel.
Description
[0001] This application is a divisional of U.S. application Ser.
No.. 13/307,392 filed Nov. 30, 2011, which is a non-provisional of
U.S. application Ser. No. 61/418,889 filed Dec. 2, 2010, both of
which are incorporated herein by reference.
DESCRIPTION
[0002] The present invention relates to the use of the reaction
product formed from (a) a hydrocarbyl-substituted dicarboxylic acid
whose hydrocarbyl radical has 8 to 250 carbon atoms, or the
anhydride thereof, and (b) a nitrogen compound of the general
formula I
##STR00002##
[0003] or a salt of the nitrogen compound I, where R.sup.1 and
R.sup.2 are each independently hydrogen or a C.sub.1- to
C.sub.20-hydrocarbyl radical,
[0004] as an additive in a fuel for reducing fuel consumption in
the operation of a spark-ignited internal combustion engine with
this fuel or as an additive in a gasoline fuel for reduction of
fuel consumption in the operation of a self-ignition internal
combustion engine with this fuel.
[0005] The present invention further relates to a fuel composition
which comprises a gasoline fuel, the reaction product mentioned and
at least one fuel additive with detergent action.
[0006] The present invention further relates to an additive
concentrate which comprises the reaction product mentioned and at
least one fuel additive with detergent action.
[0007] It is known that particular substances in the fuel reduce
internal friction in the internal combustion engines, especially in
gasoline engines, and thus help to save fuel. Such substances are
also referred to as lubricity improvers, friction reducers or
friction modifiers. Lubricity improvers customary on the market for
gasoline fuels are usually condensation products of naturally
occurring carboxylic acids such as fatty acids with polyols such as
glycerol or with alkanolamines, for example glyceryl
monooleate.
[0008] A disadvantage of the prior art lubricity improvers
mentioned is poor miscibility with other typically used fuel
additives, especially with detergent additives such as
polyisobuteneamines and/or carrier oils such as polyalkylene
oxides. An important requirement in practice is that the component
mixtures or additive concentrates provided are readily pumpable
even at relatively low temperatures, especially at outside winter
temperatures of, for example, down to -20.degree. C., and remain
homogeneously stable over a prolonged period, i.e. no phase
separation and/or precipitates may occur.
[0009] Typically, the miscibility problems outlined are avoided by
adding relatively large amounts of mixtures of paraffinic or
aromatic hydrocarbons with alcohols such as tertbutanol or
2-ethylhexanol as solubilizers to the component mixtures or
additive concentrates. In some cases, however, considerable amounts
of these expensive solubilizers are necessary in order to achieve
the desired homogeneity, and so this solution to the problem
becomes uneconomic.
[0010] The low molecular weight carboxylic acids and carboxylic
acid derivatives, glycol ethers and alkylated phenols recommended
in WO 2007/053787 as solubilizers for such component mixtures or
additive concentrates are also uneconomic owing to their high
feedstock costs and, apart from their function as solubilizers, do
not have any further positive effects. On the contrary, they harbor
the risk of causing adverse effects, for example undesired oil
dilution and increased formation of combustion chamber
deposits.
[0011] In addition, the prior art lubricity improvers mentioned
often have the tendency to form emulsions with water in the
component mixtures or additive concentrates or in the fuel itself,
such that water which has penetrated can be removed again via a
phase separation only with difficulty or at least only very
slowly.
[0012] For instance, the lubricity improvers described in EP-A 1
424 322 and WO 03/070860, which are based on
polyisobutenylsuccinimides with mono- or polyamines or
alkanolamines such as butylamine, diethylenetriamine,
tetraethylenepentamine or aminoethyleneethanolamine, exhibit good
miscibility with further additive components in corresponding
mixtures or concentrates, but have a marked tendency to form stable
emulsions with water, which can lead to the effect that water and
soil particles are entrained into the fuel supply chain and
ultimately can also get into the engine. Water can cause corrosion;
soil particles can lead to damage in fuel pumps, fuel filters and
injectors.
[0013] It was an object of the present invention to provide fuel
additives which firstly bring about effective fuel saving in the
operation of a spark-ignited internal combustion engine, and
secondly no longer have the outlined shortcomings of the prior art,
i.e. more particularly poor miscibility with other fuel additives
and the tendency to form emulsions with water. In addition, they
should not worsen the high level of intake valve cleanliness
achieved by the modern fuel additives.
[0014] Accordingly, the use, defined at the outset, of the reaction
product formed from (a) a hydrocarbyl-substituted dicarboxylic acid
or anhydride thereof and (b) a nitrogen compound of the general
formula I has been found. It can be assumed that the cause of the
fuel saving by virtue of the reaction product mentioned is based
substantially on the effect thereof as an additive which reduces
internal friction in the internal combustion engines, especially in
gasoline engines. The reaction product mentioned thus functions in
the context of the present invention essentially as a lubricity
improver.
[0015] Reaction products formed from a hydrocarbyl-substituted
dicarboxylic acid or anhydride thereof and an aminoguanidine or a
salt thereof are described in US published specifications U.S.
2009/0282731 A1 and U.S. 2010/0037514 A1 as additives for improving
the performance of diesel engines and for cleaning injectors in the
diesel engines.
[0016] British patents GB 998 869 and GB 1 020 059 disclose that
the reaction product formed from polyisobutenylsuccinic anhydride
and aminoguanidine bicarbonate is also suitable as a detergent
additive in gasoline fuels.
[0017] European published specification EP 0 310 367 A1 states that
the reaction product formed from polyisobutenylsuccinic anhydride
and aminoguanidinebicarbonate protects copper and copper alloys in
diesel engines when it is present in the motor oil.
[0018] Spark-ignition internal combustion engines are preferably
understood to mean gasoline engines, which are typically ignited
with spark plugs. In addition to the customary four- and two-stroke
gasoline engines, spark-ignition internal combustion engines also
include other engine types, for example the Wankel engine. These
are generally engines which are operated with conventional gasoline
types, especially gasoline types according to EN 228,
gasoline-alcohol mixtures such as Flex fuel with 75 to 85% by
volume of ethanol, liquid pressure gas ("LPG") or compressed
natural gas ("CNG") as fuel.
[0019] However, the inventive use of the reaction product formed
from (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride
thereof and (b) a nitrogen compound of the general formula I also
relates to newly developed internal combustion engines such as the
"HCCI" engine, which is self-igniting and is operated with gasoline
fuel.
[0020] The nitrogen compounds of the general formula I for reaction
component (a) are guanidine, substituted guanidines or salts
thereof. Possible hydrocarbyl radicals in these compounds comprise
1 to 20, especially 1 to 12 and in particular 1 to 8 carbon atoms.
A hydrocarbyl radical shall be understood here to mean a
hydrocarbyl radical of any structure which, however, in minor
amounts, may also comprise heteroatoms such as oxygen and/or
nitrogen atoms and/or halogen atoms, and/or bear functional groups
such as hydroxyl groups, carboxyl groups, carboxylic ester groups,
cyano groups, nitro groups and/or sulfo groups, provided that the
dominant hydrocarbon character of the radical is not distorted
thereby. Said hydrocarbyl radical may be saturated or unsaturated
in nature; it may have a linear or branched structure; it may
comprise aromatic and/or heterocyclic substructures.
[0021] The nitrogen compound I may have two such hydrocarbyl
radicals for R.sup.1 and R.sup.2, or only one such hydrocarbyl
radical for R.sup.1 or R.sup.2, in which latter case the other
substituent is hydrogen. Preferably, however, both substituents
R.sup.1 and R.sup.2 are hydrogen, i.e. the compound is
unsubstituted aminoguanidine.
[0022] Possible hydrocarbyl radicals for R.sup.1 and/or R.sup.2 are
preferably linear or branched alkyl or alkenyl radicals, especially
those having 1 to 8 and preferably 1 to 4 carbon atoms, such as
methyl, ethyl, vinyl, n-propyl, isopropyl, 1-propenyl, 2-propenyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl,
heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, isononyl,
decyl, neodecyl, 2-propylheptyl, undecyl, neoundecyl, dodecyl,
tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl (stearyl), oleyl, linolyl, linolenyl,
nonadecyl, eicosyl or constitutional isomers thereof.
[0023] In addition, possible hydrocarbyl radicals for R.sup.1
and/or R.sup.2 may also refer to cycloalkyl radicals, for example
cyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl or
cycloheptyl.
[0024] In addition, possible hydrocarbyl radicals for R.sup.1
and/or R.sup.2 may also be aryl, alkaryl or arylalkyl radicals, for
example, phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl,
4-phenylbutyl, tolyl or o-, m- or p-xylyl.
[0025] When the nitrogen compound I is used in the form of one of
its salts, this is especially a halide such as chloride or bromide,
carbonate, hydrogencarbonate (bicarbonate), nitrate or
orthophosphate. Preference is given to using a hydrogencarbonate
(bicarbonate).
[0026] In a preferred embodiment, the nitrogen compound of
component (b) is unsubstituted aminoguanidine
hydrogencarbonate.
[0027] The hydrocarbyl-substituted dicarboxylic acid or anhydride
thereof of component (a) typically has a saturated C.sub.2- to
C.sub.10-dicarboxylic acid or anhydride thereof as the base
skeleton. The dicarboxylic acid or anhydride thereof may bear a
plurality of, for example two or three, hydrocarbyl substituents,
but preferably only one hydrocarbyl substituent. The anhydride is
typically in cyclic form when the anhydride is formed
intramolecularly. However, open-chain anhydrides which have formed
by intermolecular anhydride formation are also suitable. Examples
of such dicarboxylic acids are oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
azelaic acid and sebacic acid. Aromatic dicarboxylic acids such as
phthalic acid or terephthalic acid are likewise suitable.
[0028] In a preferred embodiment, the hydrocarbyl-substituted
dicarboxylic acid used as reaction component (a) is based on
succinic acid or the anhydride thereof. More particularly, the
corresponding succinic anhydride of the formula II
##STR00003##
in which R.sup.3 denotes a hydrocarbyl radical having 8 to 250
carbon atoms is suitable here. A hydrocarbyl radical shall also be
understood here to mean a hydrocarbyl radical of any structure
which, however, in a minor amount, may also comprise heteroatoms
such as oxygen and/or nitrogen atoms and/or halogen atoms, and/or
bear functional groups such as hydroxyl groups, carboxyl groups,
carboxylic ester groups, cyano groups, nitro groups and/or sulfo
groups, provided that the dominant hydrocarbon character of the
radical is not distorted thereby. This hydrocarbyl radical is
typically an alkyl, alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl
or alkylaryl radical. In the case of longer-chain hydrocarbyl
radicals, it may be based on an olefin polymer, for example on a
polyethylene, polypropylene or polyisobutylene.
[0029] The hydrocarbyl radical in component (a), i.e. the R.sup.3
radical, in a preferred embodiment is a linear or branched C.sub.8-
to C.sub.40-alkyl or -alkenyl radical or a polyisobutenyl radical
having 24 to 250 carbon atoms.
[0030] Linear or branched C.sub.8- to C.sub.40-alkenyl radicals and
polyisobutenyl radicals are typically obtained by a thermal ene
reaction between the unsubstituted dicarboxylic acid or anhydride
thereof and a long-chain .alpha.-olefin to obtain an olefinic
double bond in the .alpha.,.beta. position of the hydrocarbyl side
chain. For this purpose, the reactants are heated typically to
temperatures of 150 to 250.degree. C. Alkenyl radicals can
subsequently be hydrogenated to the corresponding saturated alkyl
radicals.
[0031] Useful C.sub.8- to C.sub.40-alkenyl radicals, especially
C.sub.10- to C.sub.24-alkenyl radicals, are, for example,
1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl,
1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-octadecenyl,
1-eicosenyl, and the corresponding alkenyl radicals formed from
oligoisobutenes such as di-, tri-, tetra- or pentaisobutene, or
formed from technical .alpha.-olefin mixtures such as
C.sub.20-C.sub.24-.alpha.-olefin.
[0032] In the case of presence of a polyisobutenyl radical, it
comprises preferably 24 to 250, especially 28 to 180 and in
particular 36 to 80 carbon atoms, or thus has a number-average
molecular weight M.sub.n of preferably 330 to 3500, especially 390
to 2500, in particular 500 to 1100. Such polyisobutenyl radicals
have normally been prepared from high-reactivity polyisobutenes,
i.e. from polyisobutenes having a high proportion, typically at
least 60%, especially at least 70%, in particular at least 80%, of
terminal vinylidene double bonds.
[0033] Polyisobutenylsuccinimides ("PIBSAs") thus obtained
generally have a degree of succinylation, i.e. a molar ratio of
succinic anhydride unit to polyisobutene units, of 0.8 to 2.0,
especially of 1.0 to 1.3. It is thus also possible for two succinic
anhydride units to be bonded to one polyisobutene chain.
[0034] The reaction product obtained from (a) the
hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and
(b) the nitrogen compound I is often a mixture of several compounds
of different structure. Constituents of this mixture may especially
be imides formed from a primary amino group of I, for example the
compound IIIa, and/or compounds which comprise one or two
aminotriazole moieties, for example the compound IIIb in the case
that R.sup.1.dbd.R.sup.2.dbd.H:
##STR00004##
[0035] The inventive reaction product formed from (a) the
hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and
(b) the nitrogen compound I are outstandingly suitable as a fuel
additive which brings about an effective fuel saving in the
operation of a spark-ignition internal combustion engine,
especially of a gasoline engine, and has good miscibility with
other fuel additives and does not have any significant tendency to
form emulsions with water. The advantageous properties mentioned
are manifested to a particular degree in the case of use in
gasoline fuels with additional use of fuel additives with detergent
action.
[0036] Accordingly, the present invention also provides a fuel
composition which comprises, in a major amount, a gasoline fuel
and, in a minor amount, at least one inventive reaction product
formed from (a) a hydrocarbyl-substituted dicarboxylic acid and (b)
a nitrogen compound of the general formula I, and at least one fuel
additive which is different than the reaction product mentioned and
has detergent action.
[0037] Typically, the amount of this at least one inventive
reaction product in the gasoline fuel is 10 to 5000 ppm by weight,
more preferably 20 to 2000 ppm by weight, even more preferably 30
to 1000 ppm by weight and especially 40 to 500 ppm by weight, for
example 50 to 300 ppm by weight.
[0038] Useful gasoline fuels include all conventional gasoline fuel
compositions. A typical representative which shall be mentioned
here is the Eurosuper base fuel to EN 228, which is customary on
the market. In addition, gasoline fuel compositions of the
specification according to WO 00/47698 are also possible fields of
use for the present invention. In addition, in the context of the
present invention, gasoline fuels shall also be understood to mean
alcohol-containing gasoline fuels, especially ethanol-containing
gasoline fuels, as described, for example, in WO 2004/090079, for
example Flex fuel with an ethanol content of 75 to 85% by volume,
or gasoline fuel comprising 85% by volume of ethanol ("E85"), but
also the "E100" fuel type, which is typically azeotropically
distilled ethanol and thus consists of approx. 96% by volume of
C.sub.2H.sub.5OH and approx. 4% by volume of H.sub.2O.
[0039] The inventive reaction product formed from (a) the
hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and
(b) the nitrogen compound I may be added to the particular base
fuel either alone or in the form of fuel additive packages. Such
packages are fuel additive concentrates and generally also
comprise, as well as solvents, and as well as the at least one fuel
additive which is different than the inventive reaction product and
has detergent action, a series of further components as
coadditives, which are especially carrier oils, corrosion
inhibitors, demulsifiers, dehazers, antifoams, combustion
improvers, antioxidants or stabilizers, antistats, metallocenes,
metal deactivators, solubilizers, markers and/or dyes.
[0040] Detergents or detergent additives, referred to hereinafter
as component (D), typically refer to deposition inhibitors for
fuels. The detergent additives are preferably amphiphilic
substances which possess at least one hydrophobic hydrocarbyl
radical having a number-average molecular weight (M.sub.n) of 85 to
20 000, especially of 300 to 5000, in particular of 500 to 2500,
and at least one polar moiety.
[0041] In a preferred embodiment, the inventive fuel composition
comprises, as the at least one fuel additive which is different
than the inventive reaction product and has detergent action (D),
at least one representative which is selected from: [0042] (Da)
mono- or polyamino groups having up to 6 nitrogen atoms, at least
one nitrogen atom having basic properties; [0043] (Db) nitro
groups, optionally in combination with hydroxyl groups; [0044] (Dc)
hydroxyl groups in combination with mono- or polyamino groups, at
least one nitrogen atom having basic properties; [0045] (Dd)
carboxyl groups or their alkali metal or alkaline earth metal
salts; [0046] (De) sulfo groups or their alkali metal or alkaline
earth metal salts; [0047] (Df) polyoxy-C.sub.2-C.sub.4-alkylene
moieties terminated by hydroxyl groups, mono- or poly-amino groups,
at least one nitrogen atom having basic properties, or by carbamate
groups; [0048] (Dg) carboxylic ester groups; [0049] (Dh) moieties
derived from succinic anhydride and having hydroxyl and/or amino
and/or amido and/or imido groups; and/or [0050] (Di) moieties
obtained by Mannich reaction of substituted phenols with aldehydes
and mono- or polyamines.
[0051] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel
composition, has a number-average molecular weight (M.sub.n) of 85
to 20 000, especially of 300 to 5000, in particular of 500 to 2500.
Useful typical hydrophobic hydrocarbyl radicals, especially in
conjunction with the polar moieties (Da), (Dc), (Dh) and (Di), are
relatively long-chain alkyl or alkenyl groups, especially the
polypropenyl, polybutenyl and polyisobutenyl radicals each having
M.sub.n=300 to 5000, especially 500 to 2500, in particular 700 to
2300.
[0052] Examples of the above groups of detergent additives include
the following:
[0053] Additives comprising mono- or polyamino groups (Da) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or conventional (i.e. having predominantly internal
double bonds) polybutene or polyisobutene having M.sub.n=300 to
5000.
[0054] When the preparation of the additives proceeds from
polybutene or polyisobutene having predominantly internal double
bonds (usually in the .beta. and .gamma. positions), one possible
preparative route is by chlorination and subsequent amination or by
oxidation of the double bond with air or ozone to give the carbonyl
or carboxyl compound and subsequent amination under reductive
(hydrogenating) conditions. The amines used here for the amination
may be, for example, ammonia, monoamines or polyamines such as
dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or tetraethylenepentamine. Corresponding
additives based on polypropene are described in particular in
WO-A-94/24231.
[0055] Further preferred additives comprising monoamino groups (Da)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P=5 to
100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen,
as described in particular in WO-A-97/03946.
[0056] Further preferred additives comprising monoamino groups (Da)
are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described in particular in DE-A-196 20
262.
[0057] Additives comprising nitro groups (Db), optionally in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P=5 to
100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen
oxides and oxygen, as described in particular in WO-A-96/03367 and
in WO-A 96/03479. These reaction products are generally mixtures of
pure nitropolyisobutenes (e.g. .alpha.,.beta.-dinitropolyisobutene)
and mixed hydroxynitropolyisobutenes (e.g.
.alpha.-nitro-.beta.-hydroxypolyisobutene).
[0058] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (Dc) are in particular reaction products
of polyisobutene epoxides obtainable from polyisobutene having
preferably predominantly terminal double bonds and M.sub.n=300 to
5000, with ammonia or mono- or polyamines, as described in
particular in EP-A-476 485.
[0059] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (Dd) are preferably copolymers of
C.sub.2-C.sub.40-olefins with maleic anhydride which have a total
molar mass of 500 to 20 000 and some or all of whose carboxyl
groups have been converted to the alkali metal or alkaline earth
metal salts and any remainder of the carboxyl groups has been
reacted with alcohols or amines. Such additives are disclosed in
particular by EP-A-307 815. Such additives serve mainly to prevent
valve seat wear and can, as described in WO-A-87/01126,
advantageously be used in combination with customary fuel
detergents such as poly(iso)buteneamines or polyetheramines.
[0060] Additives comprising sulfo groups or their alkali metal or
alkaline earth metal salts (De) are preferably alkali metal or
alkaline earth metal salts of an alkyl sulfosuccinate, as described
in particular in EP-A-639 632. Such additives serve mainly to
prevent valve seat wear and can be used advantageously in
combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
[0061] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (DO are preferably polyethers or polyetheramines which are
obtainable 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-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with 1 to 30 mol of ethylene oxide
and/or propylene oxide and/or butylene oxide per hydroxyl group or
amino group and, in the case of the polyetheramines, by subsequent
reductive amination with ammonia, monoamines or polyamines. Such
products are described in particular in EP-A-310 875, EP-A-356 725,
EP-A-700 985 and U.S. Pat. No. 4,877,416. In the case of
polyethers, such products also have carrier oil properties. Typical
examples of these are tridecanol butoxylates, isotridecanol
butoxylates, isononylphenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0062] Additives comprising carboxylic ester groups (Dg) are
preferably esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, in particular those having a
minimum viscosity of 2 mm.sup.2/s at 100.degree. C., as described
in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic
acids used may be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, 6 to 24 carbon atoms. Typical
representatives of the esters are adipates, phthalates,
isophthalates, terephthalates and trimellitates of isooctanol, of
isononanol, of isodecanol and of isotridecanol. Such products also
have carrier oil properties.
[0063] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups (Dh) are preferably corresponding derivatives of
alkyl- or alkenyl-substituted succinic anhydride and especially the
corresponding derivatives of polyisobutenylsuccinic anhydride which
are obtainable by reacting conventional or high-reactivity
polyisobutene having M.sub.n=300 to 5000 with maleic anhydride by a
thermal route or via the chlorinated polyisobutene. Of particular
interest in this context are derivatives with aliphatic polyamines
such as ethylenediamine, diethylenetriamine, triethylenetetramine
or tetraethylenepentamine. The moieties having hydroxyl and/or
amino and/or amido and/or imido groups are, for example, carboxylic
acid groups, acid amides of monoamines, acid amides of di- or
polyamines which, in addition to the amide function, also have free
amine groups, succinic acid derivatives having an acid and an amide
function, carboximides with monoamines, carboximides with di- or
polyamines which, in addition to the imide function, also have free
amine groups, or diimides which are formed by the reaction of di-
or polyamines with two succinic acid derivatives. Such fuel
additives are described especially in U.S. Pat. No. 4,849,572.
[0064] The detergent additives from group (Dh) are preferably the
reaction products of alkyl- or alkenyl-substituted succinic
anhydrides, especially of polyisobutenylsuccinic anhydrides
("PIBSAs"), with amines and/or alcohols. These are thus derivatives
which are derived from alkyl-, alkenyl- or polyisobutenylsuccinic
anhydride and have amino and/or amido and/or imido and/or hydroxyl
groups. It is self-evident that these reaction products are
obtainable not only when substituted succinic anhydride is used,
but also when substituted succinic acid or suitable acid
derivatives, such as succinyl halides or succinic esters, are
used.
[0065] The additized fuel preferably comprises at least one
detergent based on a polyisobutenyl-substituted succinimide.
Especially of interest are the imides with aliphatic polyamines.
Particularly preferred polyamines are ethylenediamine,
diethylenetriamine, triethylenetetramine, pentaethylenehexamine and
in particular tetraethylenepentamine. The polyisobutenyl radical
has a number-average molecular weight M.sub.n of preferably from
500 to 5000, more preferably from 500 to 2000 and in particular of
about 1000.
[0066] Additives comprising moieties (Di) obtained by Mannich
reaction of substituted phenols with aldehydes and mono- or
polyamines are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or
polyamines such as ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols
may originate from conventional or high-reactivity polyisobutene
having M.sub.n=300 to 5000. Such "polyisobutene Mannich bases" are
described especially in EP-A-831 141.
[0067] The inventive fuel composition comprises the at least one
fuel additive which is different than the inventive reaction
product and has detergent action, and is normally selected from the
above groups (Da) to (Di), in an amount of typically 10 to 5000 ppm
by weight, more preferably of 20 to 2000 ppm by weight, even more
preferably of 30 to 1000 ppm by weight and especially of 40 to 500
ppm by weight, for example of 50 to 250 ppm by weight.
[0068] The detergent additives (D) mentioned are preferably used in
combination with at least one carrier oil. In a preferred
embodiment, the inventive fuel composition comprises, in addition
to the at least one inventive reaction product and the at least one
fuel additive which is different than the inventive reaction
product and has detergent action, as a further fuel additive in a
minor amount, at least one carrier oil.
[0069] Suitable mineral carrier oils are the fractions obtained in
crude oil processing, such as brightstock or base oils having
viscosities, for example, from the SN 500-2000 class; but also
aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
Likewise useful is a fraction which is obtained in the refining of
mineral oil and is known as "hydrocrack oil" (vacuum distillate cut
having a boiling range of from about 360 to 500.degree. C.,
obtainable from natural mineral oil which has been catalytically
hydrogenated under high pressure and isomerized and also
deparaffinized). Likewise suitable are mixtures of abovementioned
mineral carrier oils.
[0070] Examples of suitable synthetic carrier oils are selected
from: polyolefins (poly-alpha-olefins or poly(internal olefin)s),
(poly)esters, (poly)alkoxylates, polyethers, aliphatic
polyetheramines, alkylphenol-started polyethers,
alkylphenol-started polyetheramines and carboxylic esters of
long-chain alkanols.
[0071] Examples of suitable polyolefins are olefin polymers having
M.sub.n=from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or unhydrogenated).
[0072] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyetheramines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyetheramines used may be
poly-C.sub.2-C.sub.6-alkylene oxide amines or functional
derivatives thereof. Typical examples thereof are tridecanol
butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also polyisobutenol butoxylates and propoxylates,
and also the corresponding reaction products with ammonia.
[0073] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
[0074] DE-A-38 38 918. The mono-, di- or tricarboxylic acids used
may be aliphatic or aromatic acids; suitable ester alcohols or
polyols are in particular long-chain representatives having, for
example, from 6 to 24 carbon atoms. Typical representatives of the
esters are adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di(n- or isotridecyl) phthalate.
[0075] Further suitable carrier oil systems are described, for
example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0
452 328 and EP-A-0 548 617.
[0076] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having from about 5 to 35, for example
from about 5 to 30, C.sub.3-C.sub.6-alkylene oxide units, for
example selected from propylene oxide, n-butylene oxide and
isobutylene oxide units, or mixtures thereof. Nonlimiting examples
of suitable starter alcohols are long-chain alkanols or phenols
substituted by long-chain alkyl in which the long-chain alkyl
radical is in particular a straight-chain or branched
C.sub.6-C.sub.18-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0077] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-101 02 913.
[0078] Preferred carrier oils are synthetic carrier oils,
particular preference being given to polyethers.
[0079] When a carrier oil is used in addition, it is added to the
inventive additized fuel in an amount of preferably from 1 to 1000
ppm by weight, more preferably from 10 to 500 ppm by weight and in
particular from 20 to 100 ppm by weight.
[0080] In a preferred embodiment, the inventive fuel composition
comprises, in addition to the at least one inventive reaction
product, the at least one fuel additive which is different than the
inventive reaction product and has detergent action, and optionally
the at least one carrier oil, as a further fuel additive in a minor
amount, at least one corrosion inhibitor.
[0081] Corrosion inhibitors suitable as such coadditives are, for
example, succinic esters, in particular with polyols, fatty acid
derivatives, for example oleic esters, oligomerized fatty acids and
substituted ethanolamines.
[0082] Demulsifiers suitable as further coadditives are, for
example, the alkali metal and alkaline earth metal salts of
alkyl-substituted phenol- and naphthalenesulfonates and the alkali
metal and alkaline earth metal salts of fatty acid, and also
alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates,
e.g. tert-butylphenol ethoxylates or tert-pentylphenol ethoxylates,
fatty acid, alkylphenols, condensation products of ethylene oxide
and propylene oxide, e.g. ethylene oxide-propylene oxide block
copolymers, polyethyleneimines and polysiloxanes.
[0083] Dehazers suitable as further coadditives are, for example,
alkoxylated phenolformaldehyde condensates.
[0084] Antifoams suitable as further coadditives are, for example,
polyether-modified polysiloxanes.
[0085] Antioxidants suitable as further coadditives are, for
example, substituted phenols, e.g. 2,6-di-tert-butylphenol and
2,6-di-tert-butyl-3-methylphenol, and also phenylenediamines, e.g.
N,N'-di-sec-butyl-p-phenylenediamine.
[0086] Metal deactivators suitable as further coadditives are, for
example, salicylic acid derivatives, e.g.
N,N'-disalicylidene-1,2-propanediamine.
[0087] Suitable solvents, especially also for fuel additive
packages, are, for example, nonpolar organic solvents, especially
aromatic and aliphatic hydrocarbons, for example toluene, xylenes,
"white spirit" and the technical solvent mixtures of the
designations Shellsol.RTM. (manufacturer: Royal Dutch/Shell Group),
Exxol.RTM. (manufacturer: ExxonMobil) and Solvent Naphtha. Also
useful here, especially in a blend with the nonpolar organic
solvents mentioned, are polar organic solvents, in particular
alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and
2-propylheptanol.
[0088] When the coadditives and/or solvents mentioned are used in
addition in gasoline fuel, they are used in the amounts customary
therefor.
[0089] The present invention also provides an additive concentrate
which comprises at least one inventive reaction product formed from
(a) a hydrocarbyl-substituted dicarboxylic acid or anhydride
thereof and (b) a nitrogen compound of the general formula I, and
at least one fuel additive which is different than the reaction
product mentioned and has detergent action. Otherwise, the
inventive additive concentrate may comprise the further coadditives
mentioned above.
[0090] The inventive reaction product is present in the inventive
additive concentrate preferably in an amount of 1 to 99% by weight,
more preferably of 15 to 95% by weight and especially of 30 to 90%
by weight, based in each case on the total weight of the
concentrate. The at least one fuel additive which is different than
the reaction product mentioned and has detergent action is present
in the inventive additive concentrate preferably in an amount of 1
to 99% by weight, more preferably of 5 to 85% by weight and
especially of 10 to 70% by weight, based in each case on the total
weight of the concentrate.
[0091] The examples which follow are intended to further illustrate
the present invention without restricting it.
EXAMPLE 1
Mixing Performance
[0092] The reaction product ("RP1") formed from a
polyisobutenylsuccinic anhydride, obtained by thermal ene reaction
(200.degree. C.) from maleic anhydride with a polyisobutene of
number-average molecular weight M.sub.n 1000 with a content of
terminal vinylidene double bonds of 85%, and aminoguanidine
hydrogencarbonate, was prepared in analogy to Example 1 of U.S.
2009/0282731 A1, using Solvesso.TM. 150 (manufacturer: ExxonMobil)
as a diluent.
[0093] The reaction product thus prepared ("RP1") was used to
prepare an additive concentrate ("AC1") by simply mixing in the
components listed below: [0094] 400 parts by weight of the
inventive reaction product RP1 (50% by weight in Solvesso 150)
[0095] 390 parts by weight (polymer content) of a conventional
detergent additive component (polyisobutene monoamine based on a
polyisobutene with M.sub.n=1000) [0096] 310 parts by weight of a
commercial carrier oil based on an alcohol-started polyether [0097]
270 parts by weight of Solvent Naphtha as a diluent [0098] 470
parts by weight of 2-propylheptanol as a further diluent [0099] 4
parts by weight of a customary dehazer component (based on an
alkoxylated phenol-formaldehyde condensate)
[0100] It was possible to mix the components mentioned with one
another without any problem to give a clear liquid, the consistency
of which remains stable over several days.
[0101] For comparison, the additive concentrate "AC2" was prepared,
which differed from AC1 merely in that the inventive reaction
product RP1 was replaced by the same amount of active ingredient of
a commercial prior art lubricity improver ("RP2"), namely the imide
formed from polyisobutenylsuccinic anhydride (based on a
polyisobutene with M.sub.n=1000) and tetraethylenepentamine. After
mixing together, RP2 was present as a turbid liquid, from which a
precipitate separated out after a few days.
EXAMPLE 2
Emulsion Performance
[0102] A typical Eurosuper base fuel to EN 228, which is customary
on the market, was additized as a gasoline fuel in each case with
additive concentrate AC1 (inventive) and AC2 (for comparison) in
such an amount that the dosage of lubricity improver RP1
(inventive) and RP2 (for comparison) was in each case 390 ppm by
weight. According to the ASTM D 1094 phase separation test, water
was added to the systems and the phase separation behavior was
assessed. After 5 minutes, AC1 gave two clear and sharply separated
phases (phase separation rating according to ASTM D 1094: 1),
whereas, after 5 minutes, AC2 resulted in an emulsion in the water
phase and a turbid fuel phase (phase separation rating to ASTM D
1094: 4).
EXAMPLE 3
Fuel Economy
[0103] A gasoline fuel produced on the basis of a base fuel
customary on the U.S. market by additization with AC1 in the dosage
rate specified in Example 2, was used to determine fuel economy in
a fleet test with three different automobiles according to U.S.
Environmental Protection Agency Test Protocol, C.F.R. Title 40,
Part 600, Subpart B. For each automobile, the fuel consumption was
determined first with unadditized fuel and then with the same fuel
which now, however, comprised the additive concentrate AC1 in the
dosage specified in Example 2. On average, over all automobiles
used, the result was an average fuel saving of 1.3%.
EXAMPLE 4
Intake Valve Cleanliness
[0104] The intake valve deposits ("IVD") were determined to CEC
F-20-98 in a Mercedes Benz M111 engine with the two gasoline fuels
additized with AC1 (inventive) or AC2 (for comparison). Given a
base value of 94 mg per valve for the unadditized gasoline fuel,
the gasoline fuel additized with AC1 (inventive) gave a value of 2
mg per valve, and the gasoline fuel additized with AC2 (for
comparison) a value of 6 mg per valve.
* * * * *