U.S. patent application number 14/062347 was filed with the patent office on 2015-04-30 for use of polyalkylene glycol 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 Markus HANSCH, Thomas HAYDEN, Nawid KASHANI-SHIRAZI, Ludwig VOELKEL, Marc WALTER, Thomas WEISS.
Application Number | 20150113859 14/062347 |
Document ID | / |
Family ID | 51786933 |
Filed Date | 2015-04-30 |
United States Patent
Application |
20150113859 |
Kind Code |
A1 |
VOELKEL; Ludwig ; et
al. |
April 30, 2015 |
USE OF POLYALKYLENE GLYCOL TO REDUCE FUEL CONSUMPTION
Abstract
The use of a polyalkylene glycol of formula
HO--(A--O).sub.p--(CH.sub.2CH.sub.2--O).sub.m--(A--O).sub.q--H
wherein A is a C.sub.3- to C.sub.20-alkylene group or a mixture of
such alkylene groups, m is a number of from 2 to 100 and p and q
are each numbers of from 1 to 100, as an additive in a fuel for
reducing fuel consumption in the operation of an internal
combustion engine with this fuel.
Inventors: |
VOELKEL; Ludwig;
(Limburgerhof, DE) ; HANSCH; Markus; (Speyer,
DE) ; HAYDEN; Thomas; (Wappingers Falls, NY) ;
WALTER; Marc; (Frankenthal, DE) ; KASHANI-SHIRAZI;
Nawid; (Mannheim, DE) ; WEISS; Thomas;
(Ilvesheim, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
51786933 |
Appl. No.: |
14/062347 |
Filed: |
October 24, 2013 |
Current U.S.
Class: |
44/351 ; 44/370;
44/388; 44/412; 44/413; 44/432; 44/433; 44/434; 44/444 |
Current CPC
Class: |
C10L 1/1985 20130101;
C10M 145/34 20130101; C10M 2209/104 20130101; C08G 65/2609
20130101; C08G 65/331 20130101; C10N 2030/06 20130101; C10L
2200/0423 20130101; C10L 1/1608 20130101; C08L 71/02 20130101; C10L
1/2383 20130101; C10L 10/08 20130101; C08G 65/00 20130101; C10L
1/22 20130101; C10L 2270/023 20130101; C10L 1/18 20130101; C10L
1/236 20130101; C08G 2650/24 20130101; C10L 10/04 20130101; C10L
2230/22 20130101; C10L 1/1852 20130101; C10L 10/18 20130101; C10M
2209/107 20130101; C10M 2209/104 20130101; C10M 2209/105 20130101;
C10M 2209/104 20130101; C10M 2209/106 20130101; C08L 71/02
20130101; C08L 23/22 20130101 |
Class at
Publication: |
44/351 ; 44/444;
44/413; 44/432; 44/412; 44/434; 44/433; 44/388; 44/370 |
International
Class: |
C10L 10/08 20060101
C10L010/08 |
Claims
1. A method for improving performance of an internal combustion
engine, the method comprising: adding an fuel additive to fuel of
the internal combustion engine, wherein the fuel additive comprises
a polyalkylene glycol of formula I
HO--(A--O).sub.p--(CH.sub.2CH.sub.2--O).sub.m--(A--O).sub.q--H (I),
wherein A is a C.sub.3- to C.sub.20-alkylene group or a mixture
thereof, m is a number of from 2 to 100, p and q are each numbers
of from 1 to 100, and said improving is selected from the group
consisting of: reducing fuel consumption, minimizing power loss and
improving acceleration of the internal combustion engine, and
improving lubricity of lubricant oils contained in the internal
combustion engine.
2. The method of claim 1, wherein said improving is minimizing
power loss in the internal combustion engine and improving
acceleration of the internal combustion engine.
3. The method of claim 1, wherein said improving is improving
lubricity of lubricant oils contained in the internal combustion
engine by operating the internal combustion engine with a fuel
comprising an effective amount of at least one polyalkylene glycol
of formula I.
4. The method of claim 1, wherein A is a mixture of two different
types of alkylene groups A.sup.1 and A.sup.2, A.sup.1 is one or
more C.sub.3- to C.sub.7-alkylene groups, A.sup.2 is one or more
C.sub.8- to C.sub.20-alkylene groups, and A.sup.1 and A.sup.2 are
arranged randomly or blockwise.
5. The to method of claim 1, wherein A is a C.sub.8- to
C.sub.20-alkylene group (A.sup.2) or a mixture of C.sub.8- to
C.sub.20-alkylene groups (A.sup.2) arranged randomly.
6. The method of claim 1, wherein the polyalkylene glycol of
formula I is prepared by a process comprising: alkoxylating a
polyethylene glycol of formula II
HO--(CH.sub.2CH.sub.2--O).sub.m--H (II) with a C.sub.3- to
C.sub.20-alkylene oxide or a mixture thereof, thereby obtaining an
alkoxylation product, wherein: m is a number of from 2 to 100, a
molar ratio of the polyethylene glycol of formula II to the
C.sub.3- to C.sub.20-alkylene oxide or the mixture thereof is from
1:2 to 1:200, and the alkoxylation product is arranged randomly or
blockwise.
7. A fuel composition, comprising, in a major amount, a gasoline
fuel, and in a minor amount, at least one polyalkylene glycol of
formula I
HO--(A--O).sub.p--(CH.sub.2CH.sub.2--O).sub.m--(A--O).sub.q--H (I)
and at least one fuel additive which is different from the
polyalkylene glycol and has detergent action, wherein A is a
C.sub.3- to C.sub.20-alkylene group or a mixture thereof, m is a
number of from 2 to 100, and p and q are each numbers of from 1 to
100.
8. The fuel composition of claim 7, wherein the at least one fuel
additive which is different from the polyalkylene glycol and has
detergent action is at least one representative (D) selected from
the group consisting of: (Da) a mono- or polyamino group comprising
up to 6 nitrogen atoms with at least one nitrogen atom having basic
properties; (Db) a nitro group, optionally in combination with a
hydroxyl group; (Dc) a hydroxyl group in combination with a mono-
or polyamino group with at least one nitrogen atom having basic
properties; (Dd) a carboxyl group, an alkali carboxylate, or an
alkaline earth carboxylate; (De) a sulfonic acid group, an alkali
sulfonic acid salt, or an alkaline earth sulfonic acid salt; (Df) a
polyoxy-C.sub.2-C.sub.4-alkylene moiety terminated by a carbamate
group, a hydroxyl, group, or a mono- or polyamino, group with at
least one nitrogen atom having basic properties; (Dg) a carboxylic
ester group; (Dh) a moiety 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 moiety obtained by
Mannich reaction of substituted phenols with aldehydes and mono- or
polyamines.
9. The fuel composition of claim 7, further comprising, a carrier
oil as an additional fuel additive in a minor amount.
10. The fuel composition of claim 7, further comprising, tertiary
hydrocarbyl amine of formula NR.sup.1R.sup.2R.sup.3 as an
additional fuel additive in a minor amount, wherein R.sup.1,
R.sup.2 and R.sup.3 are each independently a C.sub.1- to
C.sub.20-hydro-carbyl residue with the proviso that an overall
number of carbon atoms in formula NR.sup.1R.sup.2R.sup.3 does not
exceed 30.
11. The fuel composition of claim 7, comprising: a representative
(Da), which is a polyisobutene mono- or polyamine having M.sub.n of
from 300 to 5000, comprising at least 50 mol-% of vinylidene double
bonds and prepared by hydroformylation of a polyisobutene and
subsequent reductive amination with ammonia, a monoamine or a
polyamine, and a mineral or synthetic carrier oil.
12. An additive concentrate, comprising: a polyalkylene glycol of
formula I:
HO--(A--O).sub.p-(CH.sub.2CH.sub.2--O).sub.m--(A--O).sub.q--H (I)
and a fuel additive which is different from the poly-alkylene
glycol and has detergent action, wherein A is a C.sub.3- to
C.sub.20-alkylene group or a mixture thereof, m is a number of from
2 to 100, and p and q are each numbers of from 1 to 100.
13. The additive concentrate of claim 12, comprising: a
representative (Da), which is a polyisobutene mono- or polyamine
having M.sub.n of from 300 to 5000, comprising at least 50 mol-% of
vinylidene double bonds and prepared by hydroformylation of a
polyisobutene and subsequent reductive amination with ammonia, a
monoamine or a polyamine, and a mineral or synthetic carrier oil.
Description
[0001] The present invention relates to the use of a polyalkylene
glycol of general formula I
HO--(A--O).sub.p--(CH.sub.2CH.sub.2--O).sub.m--(A--O).sub.q-H
(I)
wherein A is a C.sub.3- to C.sub.20-alkylene group or a mixture of
such alkylene groups, m is a number of from 2 to 100 and p and q
are each numbers of from 1 to 100, [0002] as an additive in a fuel
for different purposes.
[0003] The present invention further relates to a fuel composition
which comprises a gasoline fuel, the polyalkylene glycol mentioned
and at least one fuel additive with detergent action.
[0004] The present invention further relates to an additive
concentrate which comprises the polyalkylene glycol mentioned and
at least one fuel additive with detergent action.
[0005] 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.
[0006] A disadvantage of the prior art lubricity improvers
mentioned is poor miscibility with other typically used fuel
additives, especially with detergent additives such as
polyisobuteneamines and/or carrier oils such as polyalkylene
oxides. An important requirement in practice is that the component
mixtures or additive concentrates provided are readily pumpable
even at relatively low temperatures, especially at outside winter
temperatures of, for example, down to -20.degree. C., and remain
homogene-ously stable over a prolonged period, i.e. no phase
separation and/or precipitates may occur.
[0007] Typically, the miscibility problems outlined are avoided by
adding relatively large amounts of mixtures of paraffinic or
aromatic hydrocarbons with alcohols such as tert-butanol or
2-ethylhexanol as solubilizers to the component mixtures or
additive concentrates. In some cases, however, considerable amounts
of these expensive solubilizers are necessary in order to achieve
the desired homogeneity, and so this solution to the problem
becomes uneconomic.
[0008] In addition, the prior art lubricity improvers mentioned
often have the tendency to form emulsions with water in the
component mixtures or additive concentrates or in the fuel itself,
such that water which has penetrated can be removed again via a
phase separa-tion only with difficulty or at least only very
slowly.
[0009] WO 99/16849 discloses a complex ester resulting from an
esterification reaction between polyfunctional alcohols and
polyfunctional carboxylic acids using a chain stopping agent to
form ester bonds with the remaining hydroxyl or carboxyl groups,
containing as a polyfunctional carboxylic acid component dimerised
and/or trimerised fatty acids. This complex ester is recommended
for as an additive, a base fluid or a thickener in transmission
oils, hydraulic fluids, four-stroke oils, fuel additives,
com-pressor oils, greases, chain oils and for metal working rolling
applications.
[0010] WO 98/11178 discloses a polyol ester distillate fuel
additive synthesized from a polyol an a mono- or polycarboxylic
acid in such a manner that the resulting ester has uncon-erted
hydroxyl groups, such polyol ester being useful as a lubricity
additive for diesel fuel, jet fuel and kerosene.
[0011] WO 03/012015 discloses an additive for improving the
lubricity capacity of low-sulphur fuel oils, such additive
containing an ester of a bivalent or polyvalent alcohol and a
mixture of unsaturated or saturated mono- or dicarboxylic acids
whose carbon length are between 8 and 30 carbon atoms.
[0012] It was an object of the present invention to provide fuel
additives which firstly bring about effective fuel saving in the
operation of a spark-ignited internal combustion engine, and
secondly no longer have the outlined shortcomings of the prior art,
i.e. more particularly not remaining homogeneously stable over a
prolonged period without any phase separation and/or precipitates,
poor miscibility with other fuel additives and the tendency to form
emulsions with water. In addition, they should not worsen the high
level of intake valve cleanliness achieved by the modern fuel
additives.
[0013] Accordingly, the use of a polyalkylene glycol of general
formula I as described above as an additive in a fuel for reducing
fuel consumption in the operation of an internal combustion engine
with this fuel has been found. Preferably, the said use as an
additive in a gasoline fuel for reducing fuel consumption in the
operation of a spark-ignited internal combustion engine with this
fuel or as an additive in a gasoline fuel for reduction of fuel
consumption in the operation of a self-ignition internal combustion
engine with this fuel has been found.
[0014] It can be assumed that the cause of the fuel saving by
virtue of the polyalkylene glycol 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] Furthermore, the use of a polyalkylene glycol as described
above as an additive in a fuel for minimization of power loss in
internal combustion engines and for improving acceleration of
internal combustion engines has been found.
[0016] Furthermore, the use of a polylalkylene glycol as described
above as an additive in a fuel for improving the lubricity of
lubricant oils contained in an internal combustion engine for
lubricating purposes by operating the internal combustion engine
with a fuel containing an effective amount of at least one of the
said polyalkylene glycol has been found.
[0017] It can be assumed that a part of the polyalkylene glycol
mentioned contained in the fuel is transported via the combustion
chamber where the additive containing fuel is burnt into the
lubricant oils and acting there as a further lubricating agent. The
advantage of this mechanism is that the said further lubricating
agent is continuously refreshed by the fuel feeding.
[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 polyalkylene glycol
mentioned 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 instant invention works preferably with direct injection
gasoline driven combustion engines.
[0021] Variable A in general formula I comprises C.sub.3- to
C.sub.20-alkylene groups, which are normally derived from the
corresponding hydrocarbyl epoxids, i.e. the corresponding alkylene
oxides which are usually vicinal alkylene oxides such as
1,2-alkylene oxides. Examples for such alkylene oxides are
1,2-pro-pylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,
2-methyl-1,2-propylene oxide, 1,2-pentylene oxide, 1,2-hexylene
oxide, 1,2-octylene oxide, 1,2-nonylene oxide, 1,2-decylene oxide,
1,2-undecylene oxide, 1,2-dodecylene oxide, 1,2-tetradecylene
oxide, 1,2-hexadecylene oxide, 1,2-octadecylene oxide and
1,2-eicosylene oxide. Variable A may alternatively be definded for
the above examples by formula --CHR.sup.4--CHR.sup.5-- wherein
R.sup.4 and R.sup.5 may independently be hydrogen or a C.sub.1- to
C.sub.18 alkyl radical with at least one of R.sup.4 and R.sup.5
being a C.sub.1- to C.sub.18 alkyl radical and the sum of carbon
atoms in R.sup.4 and R.sup.5 not exceeding the number of 20.
[0022] Variable A in general formula I may be one single species of
alkylene groups or a mixture of different species of alkylene
groups. Such mixture may comprise three, four or preferably two
different species of alkylene groups. In case of one single species
of alkylene groups, the polyalkylene glycol mentioned is a block
copolymer of two or, if the two variables A at the two different
sides of the --(CH.sub.2CH.sub.2--O).sub.m-block are different, of
three blocks. In case of one single species of alkylene groups,
variable A normally comprises of from 8 to 20 carbon atoms. In case
of a mixture of two or of more different species of alkylene
groups, the said outward-positioned moieties HO--(A--O).sub.p-
and/or --(A--O).sub.q-H may be arranged randomly or blockwise.
[0023] In a preferred embodiment, variable A in general formula I
is a mixture of two different types of alkylene groups A.sup.1 and
A.sup.2 with A.sup.1 designating one or more C.sub.3- to
C.sub.7-alkylene groups and A.sup.2 designating one or more
C.sub.8- to C.sub.20-alkylene groups, A.sup.1 and A.sup.2 being
arranged randomly or blockwise. A.sup.1 designates preferably one
or more C.sub.3- to C.sub.6-alkylene groups, more preferably one or
more C.sub.3- to C.sub.5-alkylene groups, most preferably C.sub.3-
and/or C.sub.4-alkylene groups. A.sup.2 designates preferably one
or more C.sub.8- to C.sub.16-alkylene groups, more preferably one
or more C.sub.8- to C.sub.14-alkylene groups, most preferably one
or more C.sub.8- to C.sub.12-alkylene groups.
[0024] In another preferred embodiment, variable A in general
formula I is a C.sub.8- to C.sub.20-alkylene group (A.sup.2) or a
mixture of C.sub.8- to C.sub.20-alkylene groups (A.sup.2) arranged
randomly.
[0025] The number m of --(CH.sub.2CH.sub.2--O)-- units in the
middle of the polyalkylene glycol molecule is preferably from 2 to
50 or preferably from 3 to 75 or preferably from 4 to 100, more
preferably from 3 to 30, and most preferably from 4 to 15.
[0026] The numbers p and q, respectively, of outward-positioned
moieties --(A--O)-units are preferably each from 2 to 50, more
preferably each from 3 to 35, and most preferably each from 4 to
20.
[0027] The numbers m, p and q are mean values as a statistical
number, due to a distribution of alkoxylation homologues in the
product.
[0028] The polyalkylene glycols mentioned are preferably obtainable
by alkoxylation of polyethylene glycols of general formula II
HO--(CH.sub.2CH.sub.2--O)m--H (II)
wherein m is a number of from 2 to 100, [0029] with 2 to 200 moles
of a C.sub.3- to C.sub.20-alkylene oxide or a mixture of such
alkylene oxides per mole of polyethylene glycol II, the
alkoxylation product being arranged randomly or blockwise.
Conditions for such alkylation reactions are well known and,
therefore, do not need to be described here. Polyethylene glycols
of general formula II of different chain lengths are available from
BASF SE (among others) under the trade name of Pluriol.RTM. E.
[0030] Typical examples of polyalkylene glycols mentioned are
polyethylene glycols of general formula II with m=4 to 15 which are
alkoxylated with one or simultaneously more C.sub.8- to
C.sub.12-alkylene oxides (A.sup.2) resulting in random structures,
or which are first alkoxylated with one or more C.sub.8- to
C.sub.12-alkylene oxides (A.sup.2) and subsequently alkoxylated
with one or more C.sub.3- and/or C.sub.4-alkylene oxides (A.sup.1)
resulting in block structures regarding A.sup.1 and A.sup.2.
[0031] The polyalkylene glycol mentioned is oil soluble, which
means that, when mixed with mineral oils and/or fuels in a weight
ratio of 10:90, 50:50 and 90:10, the polyalkylene glycol does not
show phase separation after standing for 24 hours at room
temperature for at least two weight rations out of the three weight
ratios 10:90, 50:50 and 90:10.
[0032] 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 polyalkylene glycol mentioned, and at least
one fuel additive which is different from the said polyalkylene
glycols and has detergent action.
[0033] Typically, the amount of this at least one polyalkylene
glycol 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.
[0034] 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.
[0035] The polyalkylene glycol mentioned may be added to the
particular base fuel either alone or in the form of fuel additive
packages (for gasoline fuels also called "gasoline performance
packages). Such packages are fuel additive concentrates and
generally also comprise, as well as solvents, and as well as the at
least one fuel additive which is different from the said
polyalkylene glycols 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.
[0036] Detergents or detergent additives as the at least one fuel
additive which is different from the said polyalkylene glycols and
has detergent action, referred to hereinafter as component (D),
typically refer to deposition inhibitors for fuels. The detergent
additives are preferably amphiphilic substances which possess at
least one hydrophobic hydrocarbyl radical having a number-average
molecular weight (M.sub.n) of 85 to 20 000, especially of 300 to
5000, in particular of 500 to 2500, and at least one polar
moiety.
[0037] In a preferred embodiment, the inventive fuel composition
comprises, as the at least one fuel additive (D) which is different
from the said polyalkylene glycols and has detergent action, at
least one representative which is selected from: [0038] (Da) mono-
or polyamino groups having up to 6 nitrogen atoms, at least one
nitrogen atom having basic properties; [0039] (Db) nitro groups,
optionally in combination with hydroxyl groups; [0040] (Dc)
hydroxyl groups in combination with mono- or polyamino groups, at
least one nitrogen atom having basic properties; [0041] (Dd)
carboxyl groups or their alkali metal or alkaline earth metal
salts; [0042] (De) sulfo groups or their alkali metal or alkaline
earth metal salts; [0043] (Df) polyoxy-C.sub.2-C.sub.4-alkylene
moieties terminated by hydroxyl groups, mono- or polyamino groups,
at least one nitrogen atom having basic properties, or by carbamate
groups; [0044] (Dg) carboxylic ester groups; [0045] (Dh) moieties
derived from succinic anhydride and having hydroxyl and/or amino
and/or amido and/or imido groups; and/or [0046] (Di) moieties
obtained by Mannich reaction of substituted phenols with aldehydes
and mono- or polyamines.
[0047] 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.
[0048] Examples of the above groups of detergent additives include
the following: [0049] Additives comprising mono- or polyamino
groups (Da) are preferably polyalkenemono- or polyalkenepolyamines
based on polypropene or on highly-reactive (i.e. having
predominantly terminal double bonds in the .alpha.- and/or
.beta.-position such as vinylidene double bonds) or conventional
(i.e. having predominantly internal double bonds) polybutene or
polyisobutene having M.sub.n=300 to 5000. Such detergent additives
based on highly-reactive polybutene or polyisobutene, which are
normally prepared by hydroformylation of the poly(iso)butene and
subsequent reductive amination with ammonia, monoamines or
polyamines, are known from EP-A 244 616. When the preparation of
the additives proceeds from polybutene or polyisobutene having
predominantly internal double bonds (usually in the .beta.- and/or
.gamma.- positions), one possible preparative route is by
chlorination and subsequent amination or by oxidation of the double
bond with air or ozone to give the carbonyl or carboxyl compound
and subsequent amination under reductive (hydrogenating)
conditions. The amines used here for the amination may be, for
example, ammonia, monoamines or polyamines such as
dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or tetraethylenepentamine. Corresponding
additives based on polypropene are described in particular in
WO-A-94/24231.
[0050] 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.
[0051] 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.
[0052] 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).
[0053] 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.
[0054] 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.
[0055] 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.
[0056] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (Df) are preferably polyethers or polyetheramines which
are obtainable by reaction of C.sub.2-C.sub.60-alkanols,
C.sub.6-C.sub.30-alkane-diols, mono- or
di-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, isononyl-phenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0057] 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.
[0058] 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.
[0059] 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.
[0060] The additized fuel may comprise at least one detergent based
on a polyisobutenyl-substituted succinimide. Especially of interest
are the imides with aliphatic polyamines. Particularly preferred
polyamines are ethylenediamine, diethylenetriamine,
triethylenetetramine, pentaethylenehexamine and in particular
tetraethylenepentamine. The polyisobutenyl radical has a
number-average molecular weight M.sub.n of preferably from 500 to
5000, more preferably from 500 to 2000 and in particular of about
1000.
[0061] 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, di-ethylenetriamine,
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.
[0062] The inventive fuel composition comprises the at least one
fuel additive which is different from the polyalkylene glycols
mentioned and has detergent action, and is normally selected from
the above groups (Da) to (Di), in an amount of typically 10 to 5000
ppm by weight, more preferably of 20 to 2000 ppm by weight, even
more preferably of 30 to 1000 ppm by weight and especially of 40 to
500 ppm by weight, for example of 50 to 250 ppm by weight.
[0063] 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 polyalkylene glycol mentioned and the at least
one fuel additive which is different than the polyalkylene glycol
mentioned and has detergent action, as a further fuel additive in a
minor amount, at least one carrier oil.
[0064] 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.
[0065] 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. For the avoidance of doubt, the said
(poly)alkoxylates and polyethers which are suitable as synthetic
carrier oils for the instant invention, are different from the
polyalkylene glycols mentioned.
[0066] 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).
[0067] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyetheramines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyether-amines used may be
poly-C.sub.2-C.sub.6-alkylene oxide amines or functional
derivatives thereof. Typical examples thereof are tridecanol
butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also polyisobutenol butoxylates and propoxylates,
and also the corresponding reaction products with ammonia.
[0068] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; suitable ester alcohols or polyols are
in particular long-chain representatives having, for example, from
6 to 24 carbon atoms. Typical representatives of the esters are
adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di(n- or isotridecyl) phthalate.
[0069] 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.
[0070] 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.
[0071] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-101 02 913.
[0072] Preferred carrier oils are synthetic carrier oils,
particular preference being given to poly-ethers.
[0073] 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.
[0074] In a preferred embodiment, the inventive fuel composition
comprises, in addition to the at least one polyalkylene glycol
mentioned, the at least one fuel additive which is different from
the polylalkylene glycol mentioned and has detergent action, and
optionally the at least one carrier oil, as a further fuel additive
in a minor amount at least one tertiary hydrocarbyl amine of
formula NR.sup.1R.sup.2R.sup.3 wherein R.sup.1, R.sup.2 and R.sup.3
are the same or different C.sub.1- to C.sub.20-hydrocarbyl residues
with the proviso that the overall number of carbon atoms in formula
NR.sup.1R.sup.2R.sup.3 does not exceed 30.
[0075] Tertiary hydrocarbyl amines have proven to be advantageous
with regard to use as performance additives in fuels controlling
deposits. Besides their superior performance behavior, they are
also good to handle as their melting points are normally low enough
to be usually liquid at ambient temperature.
[0076] "Hydrocarbyl residue" for R.sup.1 to R.sup.3 shall mean a
residue which is essentially composed of carbon and hydrogen,
however, it can contain in small amounts heteroatomes, especially
oxygen and/or nitrogen, and/or functional groups, e.g. hydroxyl
groups and/or carboxylic groups, to an extent which does not
distort the predominantly hydrocarbon character of the residue.
Hydrocarbyl residues are preferably alkyl, alkenyl, alkinyl,
cycloalkyl, aryl, alkylaryl or arylalkyl groups. Especially
preferred hydrocarbyl residues for R.sup.1 to R.sup.3 are linear or
branched alkyl or alkenyl groups.
[0077] The overall number of carbon atoms in the tertiary
hydrocarbyl amine mentioned is at most 30, preferably at most 27,
more preferably at most 24, most preferably at most 20. Preferably,
the minimum overall number of carbon atoms in formula
NR.sup.1R.sup.2R.sup.3 is 6, more preferably 8, most preferably 10.
Such size of the tertiary hydrocarbyl amine mentioned corresponds
to molecular weight of about 100 to about 450 for the largest range
and of about 150 to about 300 for the smallest range; most usually,
tertiary hydrocarbyl amines mentioned within a molecular range of
from 100 to 300 are used.
[0078] The three C.sub.1- to C.sub.20-hydrocarbyl residues may be
identical or different. Preferably, they are different, thus
creating an amine molecular which exhibits an oleophobic moiety
(i.e. the more polar amino group) and an oleophilic moiety (i.e. a
hydrocarbyl residue with a longer chain length or a larger volume).
Such amine molecules with oleophobic/oleophilic balance have proved
to show the best deposit control performance according the present
invention.
[0079] Preferably, a tertiary hydrocarbyl amine of formula
NR.sup.1R.sup.2R.sup.3 is used wherein at least two of hydrocarbyl
residues R.sup.1, R.sup.2 and R.sup.3 are different with the
proviso that the hydrocarbyl residue with the most carbon atoms
differ in carbon atom number from the hydrocarbyl residue with the
second most carbon atoms in at least 3, preferably in at least 4,
more preferably in at least 6, most preferably in at least 8. Thus,
the tertiary amines mentioned exhibit hydrocarbyl residues of two
or three different chain length or different volume,
respectively.
[0080] Still more preferably, a tertiary hydrocarbyl amine of
formula NR.sup.1R.sup.2R.sup.3 is used wherein one or two of
R.sup.1 to R.sup.3 are C.sub.7- to C.sub.20-hydrocarbyl residues
and the remaining two or one of R.sup.1 to R.sup.3 are C.sub.1- to
C.sub.4-hydrocarbyl residues.
[0081] The one or the two longer hydrocarbyl residues, which may be
in case of two residues identical or different, exhibit from 7 to
20, preferably from 8 to 18, more preferably from 9 to 16, most
preferably from 10 to 14 carbon atoms. The one or the two remaining
shorter hydrocarbyl residues, which may be in case of two residues
identical or different, exhibit from 1 to 4, preferably from 1 to
3, more preferably 1 or 2, most preferably 1 carbon atom(s).
Besides the desired deposit controlling performance, the oleophilic
long-chain hydrocarbyl residues provide further advantageous
properties to the tertiary amines, i.e. high solubility for
gasoline fuels and low volatility.
[0082] More preferably, tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are used, wherein R.sup.1 is a C.sub.8- to
C.sub.18-hydrocarbyl residue and R.sup.2 and R.sup.3 are
independently of each other C.sub.1- to C.sub.4-alkyl radicals.
Still more preferably, tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are used, wherein R.sup.1 is a C.sub.9- to
C.sub.16-hydrocarbyl residue and R.sup.2 and R.sup.3 are both
methyl radicals.
[0083] Examples for suitable linear or branched C.sub.1- to
C.sub.20-alkyl residues for R.sup.1 to R.sup.3 are: methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert-butyl,
n-pentyl, tert-pentyl, 2-methylbutyl,
3-methylbutyl,1,1-dimethylpropyl,1,2-dimethylpropyl, n-hexyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, n-heptyl,
1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl,
5-methylhexyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl,
2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dime-thylpentyl,
2,5-dimethylpentyl, 2-diethylpentyl, 3-diethyl-pentyl, n-octyl,
1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl,
5-methylheptyl, 6-methylheptyl, 1,1-dimethylhexyl,
1,2-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl,
2,4-dimethyl-hexyl, 2,5-dimethylhexyl, 2,6-dimethylhexyl,
2-ethyl-hexyl, 3-ethylhexyl, 4-ethylhexyl, n-nonyl, iso-nonyl,
n-decyl, 1-propylheptyl, 2-propyl-heptyl, 3-propylheptyl,
n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and
eicosyl.
[0084] Examples for suitable linear or branched C.sub.2- to
C.sub.20-alkenyl and -alkinyl residues for R.sup.1 to R.sup.3 are:
vinyl, allyl, oleyl and propin-2-yl.
[0085] Tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 with long-chain alkyl and alkenyl residues
can also preferably be obtained or derived from natural sources,
i.e. from plant or animal oils and lards. The fatty amines derived
from such sources which are suitable as such tertiary hydrocarbyl
amines normally form mixtures of differents similar species such as
homologues, e.g. tallow amines containing as main components
tetradecyl amine, hexadecyl amine, octadecyl amine and octadecenyl
amine (oleyl amine). Further examples of suitable fatty amines are:
coco amines and palm amines. Unsaturated fatty amines which contain
alkenyl residues can be hydrogenated and used in this saturated
form.
[0086] Examples for suitable C.sub.3- to C.sub.20-cycloalkyl
residues for R.sup.1 to R.sup.3 are: cyclopropyl, cyclobutyl,
2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,
2,3-dimethyl-cyclohexyl, 2,4-dimethylcyclohexyl,
2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl,
3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-ethylcyclohexyl,
3-ethylcyclohexyl, 4-ethylcyclohexyl, cyclooctyl and
cyclodecyl.
[0087] Examples for suitable C.sub.7- to C.sub.20-aryl, -alkylaryl
or -arylalkyl residues for R.sup.1 to R.sup.3 are: naphthyl, tolyl,
xylyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, benzyl,
1-phenyl-ethyl, 2-phenylethyl, 3-phenylpropyl and
4-butylphenyl.
[0088] Typical examples for suitable tertiary hydrocarbyl amines of
formula NR.sup.1R.sup.2R.sup.3 are the following: [0089]
N,N-dimethyl-n-butylamine, N,N-dimethyl-n-pentylamine,
N,N-dimethyl-n-hexylamine, N,N-dimethyl-n-heptylamine,
N,N-dimethyl-n-octylamine, N,N-dimethyl-2-ethylhexyl-amine,
N,N-di-methyl-n-nonylamine, N,N-dimethyl-iso-nonylamine,
N,N-dimethyl-n-decylamine, N,N-dimethyl-2-propylheptylamine,
N,N-dimethyl-n-undecylamine, N,N-dimethyl-n-dodecylamine,
N,N-dimethyl-n-tridecylamine, N,N-dimethyl-iso-tridecyl-amine,
N,N-dimethyl-n-tetradecylamine, N,N-dimethyl-n-hexadecylamine,
N,N-di-methyl-n-octadecylamine, N,N-dimethyl-eicosylamine,
N,N-dimethyl-oleylamine; [0090] N,N-diethyl-n-heptylamine,
N,N-diethyl-n-octylamine, N,N-diethyl-2-ethylhexylamine,
N,N-diethyl-n-nonylamine, N,N-diethyl-iso-nonylamine,
N,N-diethyl-n-decylamine, N,N-diethyl-2-propylheptylamine,
N,N-diethyl-n-undecylamine, N,N-diethyl-n-dodecylamine,
N,N-diethyl-n-tridecylamine, N,N-diethyl-iso-tridecylamine,
N,N-diethyl-n-tetradecyl-amine, N,N-diethyl-n-hexadecylamine,
N,N-di-ethyl-n-octadecylamine, N,N-diethyl-eicosylamine,
N,N-diethyl-oleylamine; [0091] N,N-di-(n-propyl)-n-heptylamine,
N,N-di-(n-propyl)-n-octylamine,
N,N-di-(n-propyl)-2-ethylhexylamine, N,N-di-(n-propyl)n-nonylamine,
N,N-di-(n-propyl)-iso-nonylamine, N,N-di-(n-propyl)-n-decylamine,
N,N-di-(n-propyl)-2-propylheptylamine,
N,N-di-(n-propyl)n-undecylamine, [0092]
N,N-di-(n-propyl)-n-dodecylamine,
N,N-di-(n-propyl)-n-tri-decylamine,
N,N-di-(n-propyl)-iso-tridecylamine,
N,N-di-(n-propyl)-n-tetradecylamine,
N,N-di-(n-propyl)-n-hexadecylamine,
N,N-di-(n-propyl)-n-octadecylamine, N,N-di-(n-propyl)-eicosylamine,
N,N-di-(n-propyl)-oleylamine; [0093]
N,N-di-(n-butyl)-n-heptylamine, N,N-di-(n-butyl)-n-octylamine,
N,N-di-(n-butyl)-2-ethyl-hexylamine, N,N-di-(n-butyl)-n-nonylamine,
N,N-di-(n-butyl)-iso-nonylamine, N,N-di-(n-butyl)-n-decylamine,
N,N-di-(n-butyl)-2-propylheptylamine,
N,N-di-(n-butyl)-n-undecyl-amine, N,N-di-(n-butyl)-n-dodecylamine,
N,N-di-(n-butyl)-n-tridecylamine,
N,N-di-(n-butyl)-iso-tridecylamine,
N,N-di-(n-butyl)-n-tetradecylamine,
N,N-di-(n-butyl)-n-hexa-decylamine,
N,N-di-(n-butyl)-n-octadecylamine, N,N-di-(n-butyl)-eicosylamine,
N,N-di-(n-butyl)-oleyl-amine; [0094]
N-methyl-N-ethyl-n-heptylamine, N-methyl-N-ethyl-n-octylamine,
N-methyl-N-ethyl-2-ethylhexylamine, N-methyl-N-ethyl-n-nonylamine,
N-methyl-N-ethyl-iso-nonylamine, N-methyl-N-ethyl-n-decylamine,
N-methyl-N-ethyl-2-propylheptylamine,
N-methyl-N-ethyl-n-undecylamine, N-methyl-N-ethyl-n-dodecylamine,
N-methyl-N-ethyl-n-tridecylamine,
N-methyl-N-ethyl-iso-tridecylamine,
N-methyl-N-ethyl-n-tetradecylamine,
N-methyl-N-ethyl-n-hexadecylamine,
N-methyl-N-ethyl-n-octadecylamine, N-methyl-N-ethyl-eicosyl-amine,
N-methyl-N-ethyl-oleylamine; [0095]
N-methyl-N-(n-propyl)-n-heptylamine,
N-methyl-N-(n-propyl)-n-octylamine,
N-methyl-N-(n-propyl)-2-ethylhexylamine,
N-methyl-N-(n-propyl)-n-nonylamine,
N-methyl-N-(n-propyl)-iso-nonylamine,
N-methyl-N-(n-propyl)-n-decylamine,
N-methyl-N-(n-propyl)-2-propylheptylamine,
N-methyl-N-(n-propyl)-n-undecylamine,
N-methyl-N-(n-propyl)-n-dodecylamine,
N-methyl-N-(n-propyl)-n-tridecylamine,
N-methyl-N-(n-propyl)-iso-tri-decylamine,
N-methyl-N-(n-propyl)-n-tetradecylamine,
N-methyl-N-(n-propyl)-n-hexa-decylamine,
N-methyl-N-(n-propyl)-n-octadecylamine,
N-methyl-N-(n-propyl)-eicosyl-amine,
N-methyl-N-(n-propyl)-oleylamine; [0096]
N-methyl-N-(n-butyl)-n-heptylamine,
N-methyl-N-(n-butyl)-n-octylamine,
N-methyl-N-(n-butyl)-2-ethylhexylamine,
N-methyl-N-(n-butyl)-n-nonylamine,
N-methyl-N-(n-butyl)-iso-nonylamine,
N-methyl-N-(n-butyl)-n-decylamine,
N-methyl-N-(n-butyl)-2-propylheptyl-amine,
N-methyl-N-(n-butyl)-n-undecylamine,
N-methyl-N-(n-butyl)-n-dodecylamine,
N-methyl-N-(n-butyl)-n-tridecylamine,
N-methyl-N-(n-butyl)-iso-tridecylamine,
N-methyl-N-(n-butyl)-n-tetradecylamine,
N-methyl-N-(n-butyl)-n-hexadecylamine,
N-methyl-N-(n-butyl)-n-octadecylamine,
N-methyl-N-(n-butyl)-eicosylamine, N-methyl-N-(n-butyl)-oleylamine;
[0097] N-methyl-N,N-di-(n-heptyl)-amine,
N-methyl-N,N-di-(n-octyl)-amine,
N-methyl-N,N-di-(2-ethylhexyl)-amine,
N-methyl-N,N-di-(n-nonyl)-amine, N-methyl-N,N-di-(iso-nonyl)-amine,
N-methyl-N,N-di-(n-decyl)-amine,
N-methyl-N,N-di-(2-propylheptyl)-amine,
N-methyl-N,N-di-(n-undecyl)-amine,
N-methyl-N,N-di-(n-dodecyl)-amine,
N-methyl-N,N-di-(n-tridecyl)-amine,
N-methyl-N,N-di-(iso-tridecyl)-amine,
N-methyl-N,N-di-(n-tetra-decyl)-amine; [0098]
N-ethyl-N,N-di-(n-heptyl)-amine, N-ethyl-N,N-di-(n-octyl)-amine,
N-ethyl-N,N-di-(2-ethylhexyl)-amine,
N-ethyl-N,N-di-(n-nonyl)-amine, N-ethyl-N,N-di-(iso-nonyl)-amine,
N-ethyl-N,N-di-(n-decyl)-amine,
N-ethyl-N,N-di-(2-propylheptyl)-amine,
N-ethyl-N,N-di-(n-undecyl)-amine, N-ethyl-N,N-di-(n-dodecyl)-amine,
N-ethyl-N,N-di-(n-tridecyl)-amine,
N-ethyl-N,N-di-(iso-tridecyl)-amine,
N-ethyl-N,N-di-(n-tetradecyl)-amine; [0099]
N-(n-butyl)-N,N-di-(n-heptyl)-amine,
N-(n-butyl)-N,N-di-(n-octyl)-amine,
N-(n-butyl)-N,N-di-(2-ethylhexyl)-amine,
N-(n-butyl)-N,N-di-(n-nonyl)-amine,
N-(n-butyl)-N,N-di-(iso-nonyl)-amine,
N-(n-butyl)-N,N-di-(n-decyl)-amine,
N-(n-butyl)-N,N-di-(2-propylheptyl)-amine,
N-(n-butyl)-N,N-di-(n-undecyl)-amine,
N-(n-butyl)-N,N-di-(n-dodecyl)-amine,
N-(n-butyl)-N,N-di-(n-tridecyl)-amine, N-(n-butyl)-N,
N-di-(iso-tridecyl)-amine; [0100]
N-methyl-N-(n-heptyl)-N-(n-dodecyl)-amine,
N-methyl-N-(n-heptyl)-N-(n-octadecyl)-amine,
N-methyl-N-(n-octyl)-N-(2-ethylhexyl)-amine,
N-methyl-N-(2-ethylhexyl)-N-(n-dodecyl)-amine,
N-methyl-N-(2-propylheptyl)-N-(n-undecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-dodecyl)-amine,
N-methyl-N-(n-decyl)-N-(-tetradecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-hexadecyl)-amine,
N-methyl-N-(n-decyl)-N-(n-octadecyl)-amine,
N-methyl-N-(n-decyl)-N-oleylamine,
N-methyl-N-(n-dodecyl)-N-(iso-tridecyl)-amine,
N-methyl-N-(n-dodecyl)-N-(n-tetradecyl)-amine,
N-methyl-N-(n-dodecyl)-N-(n-hexa-decyl)-amine,
N-methyl-N-(n-dodecyl)-oleylamine;
[0101] Also suitable tertiary hydrocarbyl amines of formula
NR.sup.1R.sup.2R.sup.3 are monocyclic structures, wherein one of
the short-chain hydrocarbyl residue forms with the nitrogen atom
and with the other short-chain hydrocarbyl residue a five- or
six-membered ring. Oxygen atoms and/or further nitrogen atoms may
additionally be present in such five- or six-membered ring. In each
case, such cyclic tertiary amines carry at the nitrogen atom or at
one of the nitrogen atoms, respectively, the long-chain C.sub.7- to
C.sub.20-hydrocarbyl residue. Examples for such monocyclic tertiary
amines are N-(C.sub.7- to C.sub.20-hydrocarbyl)-piperidines,
N-(C.sub.7- to C.sub.20-hydrocarbyl)piperazines and N-(C.sub.7- to
C.sub.20-hydrocarbyl)-morpholines.
[0102] The inventive fuel composition may comprise further
customary coadditives, as described below:
[0103] 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.
[0104] 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. For the avoidance
of doubt, the said condensation products of ethylene oxide and
propylene oxide which are suitable as demusifiers for the instant
invention, are different from the polyalkylene glycols
mentioned.
[0105] Dehazers suitable as further coadditives are, for example,
alkoxylated phenol-formal-dehyde condensates.
[0106] Antifoams suitable as further coadditives are, for example,
polyether-modified poly-siloxanes.
[0107] 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 phenylenedi-amines, e.g.
N,N'-di-sec-butyl-p-phenylenediamine.
[0108] Metal deactivators suitable as further coadditives are, for
example, salicylic acid derivatives, e.g.
N,N'-disalicylidene-1,2-propanediamine.
[0109] 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.
[0110] When the coadditives and/or solvents mentioned are used in
addition in gasoline fuel, they are used in the amounts customary
therefor.
[0111] In an especially preferred embodiment, as the at least one
fuel additive (D) to be used together with the polyalkylene glycol
mentioned which is different from the said polyalkylenen glycol and
has detergent action is selected from (Da) polyisobutene monoamines
or polyisobutene polyamines having Mn=300 to 5000, having
predominantly vinylidene double bonds (normally at least 50 mol-%
of vinylidene double bonds, especially at least 70 mol-% of
vinylidene double bonds) and having been prepared by
hydroformylation of the respective polyisobutene and subsequent
reductive amination with ammonia, monoamines or polyamines. Such
polyisobutene monoamines and polyisobutene polyamines are
preferably applied in combination with at least one mineral or
synthetic carrier oil, more preferably in combination with at least
one polyether-based or polyetheramine-based carrier oil, most
preferably in combination with at least one
C.sub.6-C.sub.18-alcohol-started polyether having from about 5 to
35 C.sub.3-C.sub.6-alkylene oxide units, especially selected from
propylene oxide, n-butylene oxide and isobutylene oxide units, as
described above.
[0112] The present invention also provides an additive concentrate
which comprises at least one polyalkylene glycol mentioned, and at
least one fuel additive which is different from the said
polyalkylene glycols and has detergent action. Otherwise, the
inventive additive concentrate may comprise the further coadditives
mentioned above. In case of additive concentrates for gasoline
fuels, such additive concentrates are also called gasoline
performance packages.
[0113] The at least one polyalkylene glycol mentioned 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 from the polyalkylene glycols 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.
[0114] The polyalkylene glycol mentioned provides for quite a
series of advantages and unexpected performance and handling
improvements in view of the respective solutions proposed in the
art. Effective fuel saving in the operation of a spark-ignited
internal combustion engine is achieved. The respective fuel
additive concentrates remain homogeneously stable over a prolonged
period without any phase separation and/or precipitates.
Miscibility with other fuel additives is improved and the tendency
to form emulsions with water is suppressed. The high level of
intake valve and combustion chamber cleanliness achieved by the
modern fuel additives is not being worsened by the presence of the
polyalkylene glycol mentioned in the fuel, the level of intake
valve and combustion chamber cleanliness is even in most cases
increased. Power loss in internal combustion engines is minimized
and acceleration of internal combustion engines is improved. The
presence of the polyalkylene glycol mentioned in the fuel also
provides for an improved lubricating performance of the lubricating
oils in the internal combustion engine.
[0115] The examples which follow are intended to further illustrate
the present invention without restricting it.
EXAMPLES
Example 1: Preparation of a Polyalkylene Glycol "PAG 1"
[0116] Polyethylene glycol (m=about 4) available from BASF SE under
the trade name of Pluriol.RTM. E 200 was dried and simultaneously
reacted with 12 moles of 1,2-dodecylene oxide per mole of
polyethylene glycol and 20 moles of 1,2-butylene oxide per mole of
polyethylene oxide in the presence of sodium methoxide as an
alkoxylation catalyst at 130.degree. C., resulting in randomly
arranged outward-positioned --(A--O)-units. The polyalkylene glycol
obtained after purification proceedings by ion exchange resin,
exhibited a kinematic viscosity of 27 mm.sup.2/s at 100.degree.
C.
Example 2: Preparation of a Polyalkylene Glycol "PAG 2"
[0117] Polyethylene glycol (m=about 9) available from BASF SE under
the trade name of Pluriol.RTM. E 405 was dried and simultaneously
reacted with 12 moles of 1,2-dodecylene oxide per mole of
polyethylene glycol and 20 moles of 1,2-butylene oxide per mole of
polyethylene oxide in the presence of sodium methoxide as an
alkoxylation catalyst at 130.degree. C., resulting in randomly
arranged outward-positioned --(A--O)-units. The polyalkylene glycol
obtained after purification proceedings by ion exchange resin,
exhibited a kinematic viscosity of 27 mm.sup.2/s at 100.degree.
C.
Example 3: Storage Stability
[0118] 48.0% by weight of a customary gasoline performance package
("GPP 1") containing as detergent additive component Kerocom.RTM.
PIBA (a polyisobutene monoamine made by BASF SE, based on a
polyisobutene with M.sub.n=1000) and usual polyether-based carrier
oils, aliphatic hydrocarbons as a diluent, demulsifiers and
corrosion inhibitors in customary amounts, 37.7% by weight of
xylene and 14.3% by weight of polyalkylene glycol of Example 1
("PAG 1") above, were mixed at 20.degree. C. and stored thereafter
in a sealed glass bottle at -20.degree. C. for 42 days. At the
beginning of this storage period and then after each 7 days, the
mixture was evaluated visually and checked for possible phase
separation and precipitation. It is the aim that the mixture
remains clear ("c"), homogeneous ("h") and liquid ("l") after
storage and does not exhibit any phase separation ("ps") or
precipitation ("pr"). The following table shows the results of the
evaluations:
TABLE-US-00001 after 7 days c, h, l after 14 days c, h, l after 21
days c, h, l after 28 days c, h, l after 35 days c, h, l after 42
days c, h, l Result: pass
Example 4: Engine Cleanliness Tests
[0119] In order to demonstrate that the polyalkylene glycols
mentioned do not decrease engine cleanliness and that engine
cleanliness is in most cases even increased by the polyalkylene
glycols mentioned, the average IVD values and the TCD values were
determined with 250 mg/kg of the same gasoline performance package
("GPP 1") as used in Example 3 above containing additionally 150
mg/kg of polyalkylene glycol "PAG 1", and, for comparison, with 250
mg/kg of the same gasoline performance package without "PAG 1"
(referred to as "GPP 2"), according to CEC F-20-98 with a Mercedes
Benz M111 E engine using a customary RON 95 E10 gasoline fuel and a
customary RL-223/5 engine oil. The following table shows the
results of the deter-minations:
TABLE-US-00002 Additive average IVD [mg/valve] TCD [mg] GPP 1 3.25
4639 GPP 2 13.25 5109
* * * * *