Note: Descriptions are shown in the official language in which they were submitted.
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Low-molecular Weight Polyisobutyl-Substituted Amines as Detergent Boosters
Description
The present invention relates to a novel fuel additive composition comprising
(A) nitro-
gen-containing dispersants selected from polyisobutyl monoamines, polyisobutyl
poly-
amines, Mannich adducts of polyisobutylphenols, aldehyds and monoamines and
Mannich adducts of polyisobutylphenols, aldehyds and polyamines, (B) carrier
oils
which are substantially free of nitrogen and which are selected from synthetic
carrier
oils and mineral carrier oils, and (C) dispersant boosters selected from low-
molecular
weight polyisobutyl monoamines, polyisobutyl polyamines, Mannich adducts of
poly-
isobutylphenols, aldehyds and monoamines and Mannich adducts of
polyisobutylphe-
nols, aldehyds and polyamines. Furthermore, the present invention relates to a
gaso-
line fuel composition comprising a minor amount of the said fuel additive
composition.
Furthermore, the present invention relates to the use of such low-molecular
weight
polyisobutyl-substituted amines as dispersant boosters in internal combustion
engines
operated with gasoline containing the above detergents and the above carrier
oils.
Technical Background
Carburettors and inlet systems of automobile engines, and also injection
systems for
fuel proportioning, are subjected to increasing load due to contamination
caused by
dust particles from the air, unburned hydrocarbon residues from the combustion
cham-
ber and crankcase ventilation, and exhaust gas recycle passed to the intake
system.
These residues shift the air-to-fuel ratio during idling and in the lower
partial load re-
gion, so that the mixture becomes richer and combustion less complete and
conse-
quently the content of unburned or partly burned hydrocarbons in the exhaust
gas in-
creases and the gasoline consumption rises.
It is known that these drawbacks may be avoided through the use of fuel
additives for
cleaning the valves and carburettors or injection systems of Otto engines (cf.
e.g.: M.
Rossenbeck in "Katalysatoren, Tenside, Mineraloladditive", edited by J. Falbe,
U.
Hasserodt, page 223, G. Thieme Verlag, Stuttgart 1978).
For trouble-free running, modern Otto engines require automotive fuels having
a com-
plex set of properties which can only be guaranteed when use is made of
appropriate
gasoline additives. Such fuels usually consist of a complex mixture of
chemical com-
pounds and are characterized by physical parameters.
Fuel additives are i.a. used in order to avoid formation of deposits in the
intake system
and the intake valves of engines (keep-clean effect). On the other hand, fuel
additives
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2
may be used in order to remove deposits already formed at the valves and in
the intake
system (clean-up effect).
Aliphatic primary, secondary and tertiary monoamines with C,-C2o-alkyl
residues or C3-
C2o-cycloalkyl residues are known as dispersant additives in gasoline fuels,
preferably
in combination with Mannich-type dispersant additives, from WO 04/050806. The
said
monoamines can be used in gasoline fuels together with other dispersants
additives,
such as polyisobutyl monoamines or polyisobutyl polyamines based on
polyisobutene
with a number average molecular weight of from 600 to 5000, and with polyether
car-
rier oils, such as tridecanol butoxylate or isotridecanol butoxylate. The use
of the said
monoamines results in a reduction of injector nozzle fouling in direct
injection spark
ignition engines.
WO 03/076554 relates to the use of hydrocarbyl amines wherein the hydrocarbyl
moi-
ety has a number average molecular weight in the range of from 140 to 255 for
reduc-
ing injector nozzle fouling in direct injection spark ignition engines, either
for "keep
clean" or for "clean-up" purposes of such engines. In Fuel D of the examples
of WO
03/076554, a gasoline fuel was prepared by "dosing into the base fuel 645 ppmw
of a
commercial additive package ex BASF A.G., containing polyisobutyl monoamine
(PIBA), in which the polyisobutylene (PIB) chain has a number average
molecular
weight (MN) of approximately 1000, a polyether carrier fluid and an
antioxidant, with
further inclusion of 50 ppmw dodecylamine". Fuel D was subjected to a clean-up
test
determining the average injector diameter reduction after running a direct
injection
spark ignition engine with this Fuel.
WO 90/10051 relates to a gasoline fuel composition containing an intake valve
deposit
control additive formulation comprising (1) long-chain primary amines
exhibiting typi-
cally C6-C4o aliphatic radicals as substituents, e.g. decyl amine, dodecyl
amine (lauryl
amine), or tallow amines containing tetradecyl amine, hexadecyl amine,
octadecyl
amine and octadecenyl amine (oleyl amine), in combination with (2) fuel
dispersants
selected from polyalkylamines (such polyisobutyl amine) and Mannich bases, and
with
(3) fluidizer oils such as refined napthenic lubricating oil or a polyolefin
like polypropyl-
ene or polybutylene.
US 2007/0094922 Al relates to polyalkene amines such as polyisobutyl
monoamines
with improved applicational properties for use as additives in fuel or
lubricant composi-
tions. Suitable polyisobutyl monoamines are those derived from highly reactive
poly-
isobutenes available from BASF AG under the Glissopal brands, in particular
"Glis-
sopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn =
2300)
and mixtures thereof". The polyalkene amines such as polyisobutyl monoamines
dis-
closed in US 2007/0094922 Al can be used together with mineral carrier oils or
syn-
thetic carrier oils.
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3
US 3 898 056 discloses a mixture of high and low molecular weight hydrocarbyl
amines
for use in the automotive fuel additive area. The high molecular weight
hydrocarbyl
amines contain hydrocarbyl groups having a molecular weight between about 1900
and
5000; these amines may be conveniently prepared by reacting a corresponding
hydro-
carbyl halide with a monoamine or polyamine. The low molecular weight
hydrocarbyl
amines contain hydrocarbyl groups having a molecular weight between about 300
and
600; these amines may be also conveniently prepared by reacting a
corresponding
hydrocarbyl halide with a monoamine or polyamine. Examples for such high and
low
molecular weight hydrocarbyl amines are prepared from corresponding
polyisobuty-
lenes. The high and low molecular weight hydrocarbyl amines disclosed in US 3
898
056 can be used together with fuel soluble carrier oils such as nonvolatile
lubricating
mineral oils or polyalkoxy polyols.
The interrelationship between gasoline fuels and appropriate fuel additives in
fuel com-
positions may still be unsatisfactory as regards their intake valve clean-up
perform-
ance. It is, therefore, an object of the present invention to provide improved
fuel addi-
tive formulations which allow an efficient control of deposits formed in the
engine, es-
pecially an improved intake valve clean-up performance.
Brief Description of the Invention
It has now been observed that a fuel additive composition comprising:
(A) at least one nitrogen-containing dispersant selected from polyisobutyl
mono-
amines, polyisobutyl polyamines, Mannich adducts of polyisobutylphenols,
aldehyds
and monoamines and Mannich adducts of polyisobutylphenols, aldehyds and poly-
amines, each with a number average molecular weight MN of the polyisobutyl
group of
from 650 to 1800 Dalton,
(B) at least one carrier oil which is substantially free of nitrogen, selected
from syn-
thetic carrier oils and mineral carrier oils, and
(C) at least one dispersant booster selected from polyisobutyl monoamines,
polyiso-
butyl polyamines, Mannich adducts of polyisobutylphenols, aldehyds and
monoamines
and Mannich adducts of polyisobutylphenols, aldehyds and polyamines, each with
a
number average molecular weight MN of the polyisobutyl group of from 200 to
650 Dal-
ton,
with the proviso that the difference between the MN of the polyisobutyl group
of compo-
nent (A) and the MN of the polyisobutyl group of component (C) is more than
100 Dal-
ton, preferably is more than 250 Dalton, more preferably is in the range of
from more
than 100 to 900 Dalton and most preferably is in the range of from more than
250 to
600 Dalton,
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4
improves the intake valve clean-up performance of gasoline fuels
significantly. There-
fore, the said fuel additive composition is a first subject matter of the
instant invention.
A second subject matter of the instant invention is a fuel composition
comprising a ma-
jor amount of a liquid fuel in gasoline boiling range and a minor amount of
the above
fuel additive composition.
A third subject matter of the instant invention is the use of a polyisobutyl
monoamine, a
polyisobutyl polyamine, a Mannich adduct of a polyisobutylphenol, an aldehyd
and a
monoamine or a Mannich adduct of a polyisobutylphenol, an aldehyd and a
polyamine
(C), each with a number average molecular weight MN of the polyisobutyl group
of from
200 to 650 Dalton, as set out in Claim 1, as a dispersant booster in internal
combustion
engines operated with a liquid fuel in the gasoline boiling range containing
minor
amounts of (A) at least one nitrogen-containing dispersant selected from
polyisobutyl
monoamines, polyisobutyl polyamines, Mannich adducts of polyisobutylphenols,
alde-
hyds and monoamines and Mannich adducts of polyisobutylphenols, aldehyds and
polyamines, each with a number average molecular weight MN of the polyisobutyl
group of from 650 to 1800 Dalton, and (B) at least one carrier oil which is
substantially
free of nitrogen, selected from synthetic carrier oils and mineral carrier
oils.
Details Description of the Invention and Preferred Embodiments
The nitrogen-containing dispersant (Component A)
The polyisobutenes which are suitable for preparing the polyisobutyl
monoamines,
polyisobutenyl polyamines and polyisobutyl-substituted Mannich adducts used in
the
present invention include polyisobutenes which comprise at least about 20 mol-
%, pref-
erably at least 50 mol-%, more preferably at least 70 mol-%, most preferably
at least 80
mol-%, of the more reactive methylvinylidene isomer (i.e. with the terminal
vinylidene
double bond). Suitable polyisobutenes include those prepared using BF3
catalysts. The
preparation of such polyisobutenes in which the methylvinylidene isomer
comprises a
high percentage of the total composition is for example described in US-A
4,152,499
and US-A 4,605,808, starting either from pure isobutene or from technical C4
streams
containing high percentages of isobutene such as raffinate I.
Examples of suitable polyisobutenes having a high methylvinylidene content
include
products like Ultravis 30, a polyisobutene having a number average molecular
weight
of about 1300 and a methylvinylidene content of about 74 mol-%, and Ultravis
10, a
950 molecular weight polyisobutene having a methylvinylidene content of about
76
mol-%, both of British Petroleum. Another example of a suitable polyisobutene
having a
number average molecular weight of about 1000 and a high methylvinyliden
content is
Glissopal 1000, available from BASF SE.
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In most instances, the polyisobutene precursors are not a pure single product,
but
rather a mixture of compounds having a number average molecular weight in the
above range. Usually, the range of molecular weights distribution will be
relatively nar-
5 row having a maximum near the indicated molecular weight.
The amine component of the polyisobutyl monoamines or polyisobutyl polyamines,
respectively, may be derived from ammonia, a monoamine or a polyamine.
The monoamine or polyamine component comprises amines having from 1 to about
12
amine nitrogen atoms and from 1 to 40 carbon atoms. The carbon to nitrogen
ratio may
be between about 1:1 and about 10:1. Generally, the monoamine will contain
from 1 to
about 40 carbon atoms and the polyamine will contain from 2 to about 12 amine
nitro-
gen atoms and from 2 to about 40 carbon atoms.
The amine component may be a pure single product or a mixture of compounds
having
a major quantity of the designated amine.
When the amine component is a polyamine, it will preferably be a polyalkylene
poly-
amine, including alkylene diamine. Preferably, the alkylene group will contain
from 2 to
6 carbon atoms, more preferably from 2, 3 or 4 carbon atoms. Examples of such
poly-
amines include ethylene diamine, diethylene triamine, triethylene tetramine,
tetraethyl-
ene pentamine and pentaethylene hexamine. Preferred polyamines are ethylene
dia-
mine and diethylene triamine.
Particularly preferred polyisobutyl polyamines include polyisobutyl ethylene
diamine
and polyisobutyl diethylene triamine. The polyisobutyl group is substantially
saturated.
The polyisobutyl monoamines or polyisobutyl polyamines employed in the fuel
additive
composition of the instant invention are prepared by conventional procedures
known in
the art, especially by hydroformylation and subsequent reductive amination of
corre-
sponding highly reactive polyisobutenes, as described in EP-A 0 244 616. In
more de-
tail, highly reactive polyisobutenes having a high content of terminal
vinylidene double
bonds, especially at least 70 mol-%, more preferably at least 80 mol-%, of
terminal
vinylidene double bonds, are reacted with carbon monoxide and hydrogen in the
pres-
ence of a hydroformylation catalyst, e.g. a suitable rhodium or cobalt
catalyst, and
preferably in an inert solvent such as a hydrocarbon solvent at a temperature
in the
range of typically from 80 C to 200 C and CO/H2-pressures up to 600 bar.
Thereafter,
the oxo intermediate obtained is subjected to an reductive amination reaction
in the
presence of hydrogen, a suitable nitrogen compound , a suitable catalyst, e.g.
Raney
nickel or Raney cobalt, and preferably in an inert solvent such as a
hydrocarbon sol-
vent or an alcohol solvent at a temperature in the range of typically from 80
C to 200 C
and H2-pressures of from 80 to 300 bar.
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The amine portion of the molecule may carry one or more substituents. Thus,
the car-
bon and/or, in particular, the nitrogen atoms of the amine may carry
substituents se-
lected from hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl groups
of from
2 to about 10 carbon atoms, and monoketo, monohydroxy, mononitro, monocyano,
lower alkyl and lower alkoxy derivatives thereof. "Lower" as used herein means
a group
containing from 1 to about 6 carbon atoms. At least one of the hydrogen atoms
on one
of the basic nitrogen atoms of the polyamine may not be substituted so that at
least
one of the basic nitrogen atoms of the polyamine is a primary or secondary
amino ni-
trogen atom.
A polyamine finding use within the scope of the present invention as amine
component
for the polyisobutyl polyamines may be a polyalkylene polyamine, including
substituted
polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
Among
the polyalkylene polyamines, those containing 2 to 12 amino nitrogen atoms and
2 to
24 carbon atoms should be mentioned, in particular C2-C3 alkylene polyamines.
Pref-
erably, the alkylene group contains from 2 to 6 carbon atoms, there being
preferably
from 2 to 3 carbon atoms between the nitrogen atoms. Such groups are
exemplified by
ethylene, 1,2-propylene, 2,2-d imethylpropylene, trimethylene, 1,3-(2-hydroxy)-
propylene.
Examples of such polyamines include ethylene diamine, diethylene triamine,
di(trimethylene) triamine, 1,2-propylene diamine, 1,3-propylene diamine,
dipropylene
triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene
pentamine, pen-
taethylene hexamine, hexamethylene diamine, and 3-(N,N-dimethylamino) propyl-
amine. Such amines encompass isomers such as branched-chain polyamines and pre-
viously-mentioned substituted polyamines, including hydroxy- and hydrocarbyl-
substituted polyamines.
The amine component for the polyisobutyl monoamines or polyisobutyl polyamines
also may be derived from heterocyclic polyamines, heterocyclic substituted
amines and
substituted heterocyclic compounds, wherein the heterocycle comprises one or
more
five- to six-membered rings containing oxygen and/or nitrogen. Such
heterocyclic rings
may be saturated or unsaturated and substituted with groups as defined above.
As examples of heterocyclic compounds there may be mentioned 2-
methylpiperazine,
N-(2-hydroxyethyl)-piperazine, 1,2-bis-(N-piperazinyl)ethane, N,N'-bis(N-
piperazinyl)-
piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N-(3-
amino-
propyl)-morpholine, N-(beta-aminoethyl)piperazine, N-
(betaaminoethyl)piperidine, 3-
amino-N-ethylpiperidine, N-(betaaminoethyl) morpholine, N,N'-di(beta-
aminoethyl)-
piperazine, N,N'-di(beta-aminoethyl)imidazolidone-2, 1,3-dimethyl-5(beta-amino-
ethyl)hexahydrotriazine, N-(betaaminoethyl)-hexahydrotriazine, 5-(beta-
aminoethyl)-
1,3,5-dioxazine.
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Alternatively, the amine component for the polyisobutyl monoamines may be
derived
from a monoamine having the formula HNR'R2 wherein R' and R2 are independently
selected from the group consisting of hydrogen and hydrocarbyl of 1 to about
20 car-
bon atoms and, when taken together, R1 and R2 may form one or more five- or
six-
membered rings containing up to about 20 carbon atoms. Preferably, R1 is
hydrogen
and R2 is a hydrocarbyl group having 1 to about 10 carbon atoms. More
preferably, R1
and R2 are hydrogen. The hydrocarbyl groups may be straight-chain or branched
and
may be aliphatic, alicyclic, aromatic or combinations thereof. The hydrocarbyl
groups
may also contain one or more oxygen atoms.
Typical primary amines are exemplified by N-methylamine, N-ethylamine, N-n-
propyl-
amine, N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec.-butylamine, N-
tert.-
butylamine, N-n-pentylamine, N-cyclopentylamine, N-n-hexylamine, N-cyclohexyl-
amine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzyl-
amine, N-(2-phenylethyl)amine, 2-aminoethanol, 3-amino-1-proponal, 2-(2-amino-
ethoxy)ethanol, N-(2-methoxyethyl)amine, N-(2-ethoxyethyl)amine, and the like.
Pre-
ferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine.
Typical secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-
propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-di-sec-butylamine,
N,N-
di-n-pentylamine, N,N-di-n-hexylamine, N,N-dicyclohexylamine, N,N-
dioctylamine, N-
ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl-N-methylamine, N-
methyl-
N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N,N-di-(2-
hydroxy-
ethyl)amine, N,N-di(3-hydroxypropyl)amine, N,N-di(ethoxyethyl)amine, N,N-di-
(pro-
poxyethyl)amine, and the like. Preferred secondary amines are N,N-
dimethylamine,
N,N-diethylamine and N,N-di-n-propylamine.
Cyclic secondary amines may also be employed to form the polyisobutenyl mono-
amines or polyisobutenyl polyamines used in the instant invention. In such
cyclic com-
pounds, R1 and R2 of the formula hereinabove, when taken together, form one or
more
five- or six-membered rings containing up to about 20 carbon atoms. The ring
contain-
ing the amine nitrogen atom is generally saturated, but may be fused to one or
more
saturated or unsaturated rings. The rings may be substituted with hydrocarbyl
groups
of from 1 to about 10 carbon atoms and may contain one or more oxygen atoms.
Suitable cyclic secondary amines include piperidine, 4-methylpiperidine,
pyrrolidine,
morpholine, 2,6-dimethylmorpholine, and the like.
The number average molecular weight MN of the polyisobutyl group in the
polyisobutyl
monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich
adducts
used in the instant invention as nitrogen-containing dispersant component (A)
is in the
range of from 650 to 1800 Dalton, preferably of from 700 to 1500 Dalton, most
prefera-
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8
bly of from 750 to 1300 Dalton. As already stated for the polyisobutene
precursors, the
polyisobutyl monoamines, polyisobutyl polyamines and polyisobutyl-substituted
Man-
nich adducts are mostly not pure single products, but rather mixtures of
compounds
having number average molecular weights as indicated above. Usually, the range
of
molecular weights distribution will be relatively narrow having a maximum near
the in-
dicated molecular weight.
In an especially preferred embodiment, dispersant component (A) is a
polyisobutyl
monoamine with a number average molecular MN weight of the polyisobutyl group
of
from 650 to 1800 Dalton, preferably of from 700 to 1500, most preferably of
from 750 to
1300. The said polyisobutyl monoamine is preferably based on ammonia and/or
pref-
erably prepared by hydroformylation and subsequent reductive amination of
corre-
sponding highly reactive polyisobutenes, as described in EP-A 0 244 616. In
more de-
tail, highly reactive polyisobutenes having a high content of terminal
vinylidene double
bonds, especially at least 70 mol-%, more preferably at least 80 mol-%, of
terminal
vinylidene double bonds, are reacted with carbon monoxide and hydrogen in the
pres-
ence of a hydroformylation catalyst, e.g. a suitable rhodium or cobalt
catalyst, and
preferably in an inert solvent such as a hydrocarbon solvent at a temperature
in the
range of typically from 80 C to 200 C and CO/H2-pressures up to 600 bar.
Thereafter,
the oxo intermediate obtained is subjected to an reductive amination reaction
in the
presence of hydrogen, a suitable nitrogen compound, a suitable catalyst, e.g.
Raney
nickel or Raney cobalt, and preferably in an inert solvent such as a
hydrocarbon sol-
vent or an alcohol solvent at a temperature in the range of typically from 80
C to 200 C
and H2-pressures of from 80 to 300 bar.
Mannich adducts which are suitable as component (A) for the instant invention
can be
produced by reacting (i) 1 to 2 moles of at least one polyisobutylphenol which
may
carry at the aromatic ring system in addition to the polyisobutyl substituent
with a num-
ber average molecular weight MN of from 650 to 1800 Dalton, being derived
preferably
from highly reactive polyisobutene a as defined above, one or more, e.g. one,
two or
three, C1 to C7alkyl substituents such as methyl, ethyl, n-propyl, iso-propyl,
n-butyl,
iso-butyl, sec.-butyl, tert.-butyl, n-pentyl or n-hexyl, with (ii) 1 to 3
moles of at least one
C1 to C6 aldehyd such as formaldehyd, acetaldehyd and propionaldehyd which may
be
used in an oligomeric or polymeric form such as paraformaldehyd, and with
(iii) 1 to 3
moles of at least one primary or secondary amine of formula HNR3R4 in which R3
de-
notes hydrogen, a C, to C2o alkyl residue or a C3 to C20 cycloalkyl residue
and R4 de-
notes a C, to C2o alkyl residue or a C3 to C20 cycloalkyl residue, whereby
both residues
R3 and R4 can form together with the nitrogen atom they are attached to a ring
system
and/or can be independently from each other interrupted by one or more oxygen
atoms
and/or imino groups of formula -NR5- with R5 denoting hydrogen or a C, to C4
alkyl
group, and/or R4 can be terminated by a second -NH2 group. Such Mannich
adducts
are known in the art, e.g. from WO 04/050806.
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Examples for linear and branched primary amines of formula HNR3R4 are
methylamine,
ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec.-
butyl-
amine, tert.-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-
octylamine, 2-
ethylhexylamine, n-nonylamine, 3-propylheptylamine, n-decylamine, n-
undecylamine,
n-dodecylamine, n-tridecylamine, iso-tridecylamine, n-tetradecylamine, n-
pentadecyl-
amine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine
and n-eicosylamine.
Examples for linear, branched and cyclic secondary amines of formula HNR3R4
are
dimethylamine, diethylamine, di n-propylamine, di-iso-propylamine, di-n-
butylamine, di-
iso-butylamine, di-sec.-butyl-amine, di-tert.-butylamine, di-n-pentylamine, di-
n-hexyl-
amine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di-n-
nonylamine, di-
(3-propylheptyl)amine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine,
di-n-
tridecylamine, di-iso-tridecylamine, di-n-tetradecylamine, di-n-pentadecyl-
amine, di-n-
hexadecylamine, di-n-heptadecylamine, di-n-octadecylamine, di-n-
nonadecylamine, di-
n-eicosylamine, cyclooctylamine and cyclodecylamine.
Examples for amines of formula HNR3R4 which are interrupted by imino groups of
for-
mula -NR5- and/or can be terminated by a second -NH2 group are N-(3,3-
dimethylami-
no)propylamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-
butylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine and
pentaethylene-
hexamine.
Typical examples for Mannich adducts suitable as component (A) are the
reaction pro-
ducts of (i) 1 mole of 4-polyisobutylphenol (MN of the polyisobutyl group =
1000) with (ii)
1 mole of paraformaldehyd and (iii) 1 mole of dimethylamine or di-n-butylamine
or di(2-
ethylhexyl)amine. Further typical examples for Mannich adducts suitable as
component
(A) are the reaction products of (i) 2 moles of 4-polyisobutylphenol (MN of
the polyiso-
butyl group = 1000) with (ii) 2 moles of paraformaldehyd and (iii) 1 mole of
methyl-
amine or n-butylamine or 2-ethylhexylamine or 3-(N,N-
dimethylamino)propylamine.
The carrier oil (Component B)
The fuel-soluble, non-volatile carrier oil of component (B) is to be used as a
necessary
part of the fuel additive composition of the instant invention, in order to
achieve the
desired improvement in intake valve clean-up performance. The carrier oil is a
chemi-
cally inert hydrocarbon-soluble liquid vehicle. The carrier oil of component
(B) may be a
synthetic oil or a mineral oil; for the instant invention, a refined petroleum
oil is also
understood to be a mineral oil.
Such carrier oils (also called carrier fluids) are believed to act as a
carrier for the fuel
additives and to assist in removing and retarding deposits. The carrier oil
(B) may also
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WO 2011/151207 PCT/EP2011/058313
exhibit synergistic deposit control and deposit removing properties when used
in com-
bination with components (A) and (C) of the instant fuel additive composition.
The carrier oil of component (B) is typically employed in amounts ranging from
about
5 50 to about 2,000 ppm by weight of the gasoline fuel, preferably from 100 to
800 ppm
of the gasoline fuel. Preferably, the ratio of carrier oil (B) to nitrogen-
containing dis-
persant (A) in the fuel additive composition as well as in the gasoline fuel
will range
from 0.5 : 1 to 10 : 1, typically from 1 : 1 to 4 : 1.
10 When employed in fuel additive compositions or fuel additive concentrates,
such as in
the instant fuel additive composition, carrier oils will generally be present
in amounts
ranging from about 10 to about 60 weight percent, preferably from 20 to 40
weight per-
cent (referring to the amount of all components in the composition or
concentrate, re-
spectively, including possible solvents).
Examples for suitable mineral carrier oils are in particular those of
viscosity class Sol-
vent Neutral (SN) 500 to 2000, as well as aromatic and paraffinic hydrocarbons
and
alkoxyalkanols. Another useful mineral carrier oil is a fraction known as
"hydrocrack oil"
which is obtained from refined mineral oil (boiling point of approximately 360
to 500 C;
obtainable from natural mineral oil which is isomerized, freed of paraffin
components
and catalytically hydrogenated under high pressure).
Examples for synthetic carrier oils which can be used for the instant
invention are olefin
polymers with a number average molecular weight of from 400 to 1800, based on
poly-
alpha-olefins or poly-internal-olefins, especially those based on polybutene
or on poly-
isobutene (hydrogenated or non-hydrogenated). Further examples for suitable
syn-
thetic carrier oils are polyesters, polyalkoxylates, polyethers, alkylphenol-
initiated poly-
ethers, and carboxylic acids of long-chain alkanols.
Examples for suitable polyethers which can be used for the instant invention
are com-
pounds containing polyoxy-C2-C4-alkylene groups, especially polyoxy-C3-C4-
alkylene
groups, which can be obtained by reacting C1-C3o-alkanols, C2-C60-alkandiols,
C1-C30-
alkylcyclohexanols or C1-C3o-alkylphenols with 1 to 30 mol ethylene oxide
and/or pro-
pylene oxide and/or butylene oxides per hydroxyl group, especially with 1 to
30 mol
propylene oxide and/or butylene oxides per hydroxyl group. This type of
compounds is
described, for example, in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A
4,877,416.
Typical examples for suitable polyethers are tridecanol butoxylates,
isotridecanol bu-
toxylates, isononylphenol butoxylates, polyisobutenol butoxylates and
polyisobutenol
propoxylates.
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Hydrocarbyl-terminated poly(oxyalkylene) polymers which may be employed in the
pre-
sent invention as component (B), are monohydroxy compounds, i.e., alcohols,
and are
often termed monohydroxy polyethers, or polyalkylene glycol
monohydrocarbylethers,
or "capped" poly(oxyalkylene).
The hydrocarbyl-terminated poly(oxyalkylene) alcohols may be produced by the
addi-
tion of lower alkylene oxides, such as ethylene oxide, propylene oxide, the
butylene
oxides, or the pentylene oxides to the hydroxy compound under polymerization
condi-
tions. Methods of production and properties of these polymers are disclosed in
U.S.
Patents Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia of
Chemical
Technology", 2nd Ed. Volume 19, p. 507. In the polymerization reaction, a
single type
of alkylene oxide may be employed, e.g., propylene oxide, in which case the
product is
a homopolymer, e.g., a poly(oxyalkylene) propanol. However, copolymers are
equally
satisfactory and random copolymers are readily prepared by contacting the
hydroxyl-
containing compound with a mixture of alkylene oxides, such as a mixture of
propylene
and butylene oxides. Block copolymers of oxyalkylene units also provide
satisfactory
poly(oxyalkylene) polymers for the practice of the present invention. Random
polymers
are more easily prepared when the reactivities of the oxides are relatively
equal. In
certain cases, when ethylene oxide is copolymerized with other oxides, the
higher reac-
tion rate of ethylene oxide makes the preparation of random copolymers
difficult. In
either case, block copolymers can be prepared. Block copolymers are prepared
by
contacting the hydroxyl-containing compound with first one alkylene oxide,
then the
others in any order, or repetitively, under polymerization conditions. A
particular block
copolymer is represented by a polymer prepared by polymerizing propylene oxide
on a
suitable monohydroxy compound to form a poly(oxypropylene) alcohol and then po-
lymerizing butylene oxide on the poly(oxyalkylene) alcohol.
In general, the poly(oxyalkylene) polymers are mixtures of compounds that
differ in
polymer chain length. However, their properties closely approximate those of
the poly-
mer represented by the average composition and molecular weight.
Examples of carboxylic esters of long-chain alkanols are esters of mono-, di-
and tri-
carboxylic acids with long-chain alkanols or polyhydric alcohols such as
described e.g.
in DE-A 38 38 918. Suitable mono-, di- and tricarboxylic acids are aliphatic
or aromatic
carboxylic acids. Suitable alkanols and polyhydric alcohols contain 6 to 24
carbon at-
oms. Typical examples of such esters are the adipates, phthalates, iso-
phthalates,
terephthalates and trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol,
e.g. di-n-tridecyl phthalate or di-iso-tridecyl phthalate.
Examples for particularly useful synthetic carrier oils are alcohol-initiated
polyethers
containing about 5 to 35, e.g. 5 to 30 C3-C6-alkylenoxide units, such as
propylenoxide,
n-butylenoxide and iso-butylenoxide units or mixtures thereof. Non-limiting
examples
for alcoholic starters are long-chain alkanols or phenols substituted by long-
chain alkyl
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12
groups, where the alkyl group preferably is linear or branched C6-C18-alkyl.
Preferred
examples for the alcoholic starters are tridecanol and nonylphenol.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, such as
described
e.g. in DE-A 10 102 913.
Preferably, synthetic carrier oils are used. Preferred synthetic carrier oils
are alkanol
alkoxylates, in particular alkanol propoxylates and alkanol butoxylates.
In an especially preferred embodiment, carrier oil component (B) comprises at
least
one polyether obtained from C,-C3o-alkanols, especially C6-C,8-alkanols, or C2-
C60-
alkandiols, especially C8-C24-alkandiols, and from 1 to 30 mol, especially 5
to 30 mol, in
sum, of propylene oxide and/or butylene oxides. Other synthetic carrier oils
and/or
mineral carrier oils may be present in component (B) in minor amounts.
The dispersant booster (Component C)
The polyisobutenes which are suitable for preparing the low-molecular weight
polyiso-
butyl-substituted amine dispersant boosters used in the present invention as
compo-
nent (C) can include polyisobutenes which comprise at least about 20%,
preferably at
least 50%, more preferably at least 70 mol-%, most preferably at least 80 mol-
%, of the
more reactive methylvinylidene isomer (i.e. with the terminal vinylidene
double bond).
Suitable polyisobutenes include those prepared using BF3 catalysts. The
preparation of
such polyisobutenes in which the methylvinylidene isomer comprises a high
percent-
age of the total composition is for example described in US-A 4,152,499 and US-
A
4,605,808, starting either from pure isobutene or from technical C4 streams
containing
high percentages of isobutene such as raffinate I.
Furthermore, such polyisobutene suitable for preparing the low-molecular
weight poly-
isobutyl-substituted amine dispersant boosters used in the present invention
as com-
ponent (C) can bei oligomers of isobutene, e.g. triisobutene, tetraisobutene,
pentaiso-
butene, hexaisobutene, heptaisobutene, octaisobutene, nonaisobutene, decaisobu-
tene, undecaisobutene, dodecaisobutene or mixtures thereof.
In most instances, the above polyisobutene precursors are not a pure single
product,
but rather a mixture of compounds having an number average molecular weight in
the
above range of 200 to 650 Dalton. Usually, the range of molecular weights
distribution
will be relatively narrow having a maximum near the indicated molecular
weight.
The amine component of the said low-molecular weight polyisobutyl monoamines
or
polyisobutyl polyamines, respectively, may be derived from ammonia, a
monoamine or
a polyamine.
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The monoamine or polyamine component comprises amines having from 1 to about
12
amine nitrogen atoms and from 1 to 40 carbon atoms. The carbon to nitrogen
ratio may
be between about 1:1 and about 10:1. Generally, the monoamine will contain
from 1 to
about 40 carbon atoms and the polyamine will contain from 2 to about 12 amine
nitro-
gen atoms and from 2 to about 40 carbon atoms.
The amine component may be a pure single product or a mixture of compounds
having
a major quantity of the designated amine.
When the amine component is a polyamine, it will preferably be a polyalkylene
poly-
amine, including alkylene diamine. Preferably, the alkylene group will contain
from 2 to
6 carbon atoms, more preferably from 2, 3 or 4 carbon atoms. Examples of such
poly-
amines include ethylene diamine, diethylene triamine, triethylene tetramine,
tetraethyl-
ene pentamine and pentaethylene hexamine. Preferred polyamines are ethylene
dia-
mine and diethylene triamine.
Particularly preferred polyisobutyl polyamines include polyisobutyl ethylene
diamine
and polyisobutyl diethylene triamine. The polyisobutyl group is substantially
saturated.
The polyisobutyl monoamines or polyisobutyl polyamines employed in the fuel
additive
composition of the instant invention as component (C) are prepared by
conventional
procedures known in the art, especially by hydroformylation and subsequent
reductive
amination of corresponding highly reactive polyisobutenes, e.g. in analogy to
the teach-
ings of EP-A 0 244 616. In more detail, highly reactive polyisobutenes having
a high
content of terminal vinylidene double bonds, especially at least 70 mol-%,
more pref-
erably at least 80 mol-%, of terminal vinylidene double bonds, are reacted
with carbon
monoxide and hydrogen in the presence of a hydroformylation catalyst, e.g. a
suitable
rhodium or cobalt catalyst, and preferably in an inert solvent such as a
hydrocarbon
solvent at a temperature in the range of typically from 80 C to 200 C and
CO/H2-
pressures up to 600 bar. Thereafter, the oxo intermediate obtained is
subjected to an
reductive amination reaction in the presence of hydrogen, a suitable nitrogen
com-
pound , a suitable catalyst, e.g. Raney nickel or Raney cobalt, and preferably
in an
inert solvent such as a hydrocarbon solvent or an alcohol solvent at a
temperature in
the range of typically from 80 C to 200 C and H2-pressures of from 80 to 300
bar.
The amine portion of the molecule may carry one or more substituents. Thus,
the car-
bon and/or, in particular, the nitrogen atoms of the amine may carry
substituents se-
lected from hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl groups
of from
2 to about 10 carbon atoms, and monoketo, monohydroxy, mononitro, monocyano,
lower alkyl and lower alkoxy derivatives thereof. "Lower" as used herein means
a group
containing from 1 to about 6 carbon atoms. At least one of the hydrogen atoms
on one
of the basic nitrogen atoms of the polyamine may not be substituted so that at
least
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14
one of the basic nitrogen atoms of the polyamine is a primary or secondary
amino ni-
trogen atom.
A polyamine finding use within the scope of the present invention as amine
component
for the polyisobutyl polyamines may be a polyalkylene polyamine, including
substituted
polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
Among
the polyalkylene polyamines, those containing 2 to 12 amino nitrogen atoms and
2 to
24 carbon atoms should be mentioned, in particular C2-C3 alkylene polyamines.
Pref-
erably, the alkylene group contains from 2 to 6 carbon atoms, there being
preferably
from 2 to 3 carbon atoms between the nitrogen atoms. Such groups are
exemplified by
ethylene, 1,2-propylene, 2,2-d imethylpropylene, trimethylene, 1,3-(2-hydroxy)-
propylene.
Examples of such polyamines include ethylene diamine, diethylene triamine,
di(trimethylene) triamine, 1,2-propylene diamine, 1,3-propylene diamine,
dipropylene
triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene
pentamine, pen-
taethylene hexamine. hexamethylene diamine, and 3-(N,N-dimethylamino) propyl-
amine. Such amines encompass isomers such as branched-chain polyamines and pre-
viously-mentioned substituted polyamines, including hydroxy- and hydrocarbyl-
substituted polyamines.
The amine component for the polyisobutyl monoamines or polyisobutyl polyamines
also may be derived from heterocyclic polyamines, heterocyclic substituted
amines and
substituted heterocyclic compounds, wherein the heterocycle comprises one or
more
five- or six-membered rings containing oxygen and/or nitrogen. Such
heterocyclic rings
may be saturated or unsaturated and substituted with groups as defined above.
As examples of heterocyclic compounds there may be mentioned 2-
methylpiperazine,
N-(2-hydroxyethyl)-piperazine, 1,2-bis-(N-piperazinyl)ethane, N,N'-bis(N-
piperazinyl)-
piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N-(3-
amino-
propyl)-morpholine, N-(beta-aminoethyl)piperazine, N-
(betaaminoethyl)piperidine, 3-
amino-N-ethylpiperidine, N-(betaaminoethyl) morpholine, N,N'-di(beta-
aminoethyl)-
piperazine, N,N'-di(beta-aminoethyl)imidazolidone-2, 1,3-dimethyl-5(beta-amino-
ethyl)hexahydrotriazine, N-(betaaminoethyl)-hexahydrotriazine, 5-(beta-
aminoethyl)-
1,3,5-dioxazine.
Alternatively, the amine component for the polyisobutyl monoamines may be
derived
from a monoamine having the formula HNR1R2 wherein R1 and R2 are independently
selected from the group consisting of hydrogen and hydrocarbyl of 1 to about
20 car-
bon atoms and, when taken together, R1 and R2 may form one or more five- or
six-
membered rings containing up to about 20 carbon atoms. Preferably, R1 is
hydrogen
and R2 is a hydrocarbyl group having 1 to about 10 carbon atoms. More
preferably, R1
and R2 are hydrogen. The hydrocarbyl groups may be straight-chain or branched
and
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may be aliphatic, alicyclic, aromatic or combinations thereof. The hydrocarbyl
groups
may also contain one or more oxygen atoms.
Typical primary amines are exemplified by N-methylamine, N-ethylamine, N-n-
propyl-
5 amine, N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec.-butylamine,
N-tert.-
butylamine, N-n-pentylamine, N-cyclopentylamine, N-n-hexylamine, N-cyclohexyl-
amine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzyl-
amine, N-(2-phenylethyl)amine, 2-aminoethanol, 3-amino-1-proponal, 2-(2-amino-
ethoxy)ethanol, N-(2-methoxyethyl)amine, N-(2-ethoxyethyl)amine, and the like.
Pre-
10 ferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine.
Typical secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-
propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-di-sec-butylamine,
N,N-
di-n-pentylamine, N,N-di-n-hexylamine, N,N-dicyclohexylamine, N,N-
dioctylamine, N-
15 ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl-N-methylamine, N-
methyl-
N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N,N-di-(2-
hydroxy-
ethyl)amine, N,N-di(3-hydroxypropyl)amine, N,N-di(ethoxyethyl)amine, N,N-di-
(pro-
poxyethyl)amine, and the like. Preferred secondary amines are N,N-
dimethylamine,
N,N-diethylamine and N,N-di-n-propylamine.
Cyclic secondary amines may also be employed to form the polyisobutenyl mono-
amines or polyisobutenyl polyamines used in the instant invention. In such
cyclic com-
pounds, R1 and R2 of the formula hereinabove, when taken together, form one or
more
five- or six-membered rings containing up to about 20 carbon atoms. The ring
contain-
ing the amine nitrogen atom is generally saturated, but may be fused to one or
more
saturated or unsaturated rings. The rings may be substituted with hydrocarbyl
groups
of from 1 to about 10 carbon atoms and may contain one or more oxygen atoms.
Suitable cyclic secondary amines include piperidine, 4-methylpiperidine,
pyrrolidine,
morpholine, 2,6-dimethylmorpholine, and the like.
The number average molecular weight MN of the polyisobutyl group in the
polyisobutyl
monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich
adducts
used in the instant invention as dispersant booster component (C) is in the
range of
from 200 to 650 Dalton, preferably of from 250 to 600 Dalton, most preferably
of from
300 to 550 Dalton. As already stated for the polyisobutene precursors, the
polyisobutyl
monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich
adducts
are mostly not pure single products, but rather mixtures of compounds having
number
average molecular weights as indicated above. Usually, the range of molecular
weights
distribution will be relatively narrow having a maximum near the indicated
molecular
weight.
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In an especially preferred embodiment, dispersant booster component (C) is a
polyiso-
butyl monoamine with a number average molecular weight MN of the polyisobutyl
group
of from 200 to 650 Dalton, preferably of from 250 to 600 Dalton, most
preferably of
from 300 to 550. The said polyisobutyl monoamine is preferably based on
ammonia
and/or preferably prepared by hydroformylation and subsequent reductive
amination of
corresponding highly reactive polyisobutenes, as described in EP-A 0 244 616.
In more
detail, highly reactive polyisobutenes having a high content of terminal
vinylidene dou-
ble bonds, especially at least 70 mol-%, more preferably at least 80 mol-%, of
terminal
vinylidene double bonds, are reacted with carbon monoxide and hydrogen in the
pres-
ence of a hydroformylation catalyst, e.g. a suitable rhodium or cobalt
catalyst, and
preferably in an inert solvent such as a hydrocarbon solvent at a temperature
in the
range of typically from 80 C to 200 C and CO/H2-pressures up to 600 bar.
Thereafter,
the oxo intermediate obtained is subjected to an reductive amination reaction
in the
presence of hydrogen, a suitable nitrogen compound, a suitable catalyst, e.g.
Raney
nickel or Raney cobalt, and preferably in an inert solvent such as a
hydrocarbon sol-
vent or an alcohol solvent at a temperature in the range of typically from 80
C to 200 C
and H2-pressures of from 80 to 300 bar.
Mannich adducts which are suitable as component (C) for the instant invention
can be
produced by reacting (i) 1 to 2 moles of at least one polyisobutylphenol which
may
carry at the aromatic ring system in addition to the polyisobutyl substituent
with a num-
ber average molecular weight MN of from 200 to 650 Dalton, being derived
preferably
from highly reactive polyisobutene a as defined above, one or more, e.g. one,
two or
three, C1 to C7alkyl substituents such as methyl, ethyl, n-propyl, iso-propyl,
n-butyl,
iso-butyl, sec.-butyl, tert.-butyl, n-pentyl or n-hexyl, with (ii) 1 to 3
moles of at least one
C1 to C6 aldehyd such as formaldehyd, acetaldehyd and propionaldehyd which may
be
used in an oligomeric or polymeric form such as paraformaldehyd, and with
(iii) 1 to 3
moles of at least one primary or secondary amine of formula HNR3R4 in which R3
de-
notes hydrogen, a C1 to C2o alkyl residue or a C3 to C20 cycloalkyl residue
and R4 de-
notes a C, to C2o alkyl residue or a C3 to C20 cycloalkyl residue, whereby
both residues
R3 and R4 can form together with the nitrogen atom they are attached to a ring
system
and/or can be independently from each other interrupted by one or more oxygen
atoms
and/or imino groups of formula -NR5- with R5 denoting hydrogen or a C, to C4
alkyl
group, and/or R2 can be terminated by a second -NH2 group. Such Mannich
adducts
are known in the art, e.g. from WO 04/050806.
Examples for linear and branched primary amines of formula HNR3R4 are
methylamine,
ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec.-
butyl-
amine, tert.-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-
octylamine, 2-
ethylhexylamine, n-nonylamine, 3-propylheptylamine, n-decylamine, n-
undecylamine,
n-dodecylamine, n-tridecylamine, iso-tridecylamine, n-tetradecylamine, n-
pentadecyl-
amine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine
and n-eicosylamine.
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17
Examples for linear, branched and cyclic secondary amines of formula HNR3R4
are
dimethylamine, diethylamine, di n-propylamine, di-iso-propylamine, di-n-
butylamine, di-
iso-butylamine, di-sec.-butyl-amine, di-tert.-butylamine, di-n-pentylamine, di-
n-hexyl-
amine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di-n-
nonylamine, di-
(3-propylheptyl)amine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine,
di-n-
tridecylamine, di-iso-tridecylamine, di-n-tetradecylamine, di-n-pentadecyl-
amine, di-n-
hexadecylamine, di-n-heptadecylamine, di-n-octadecylamine, di-n-
nonadecylamine, di-
n-eicosylamine, cyclooctylamine and cyclodecylamine.
Examples for amines of formula HNR3R4 which are interrupted by imino groups of
for-
mula -NR5- and/or can be terminated by a second -NH2 group are N-(3,3-
dimethylami-
no)propylamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-
butylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine and
pentaethylene-
hexamine.
Typical examples for Mannich adducts suitable as component (A) are the
reaction pro-
ducts of (i) 1 mole of 4-polyisobutylphenol (MN of the polyisobutyl group =
420) with (ii)
1 mole of paraformaldehyd and (iii) 1 mole of dimethylamine or di-n-butylamine
or di(2-
ethylhexyl)amine. Further typical examples for Mannich adducts suitable as
component
(A) are the reaction products of (i) 2 moles of 4-polyisobutylphenol (MN of
the polyiso-
butyl group = 420) with (ii) 2 moles of paraformaldehyd and (iii) 1 mole of
methylamine
or n-butylamine or 2-ethylhexylamine or 3-(N,N-dimethylamino)propylamine.
In the fuel additive composition of the instant invention, dispersant
component (A) can
be a polyisobutyl monoamine, a polyisobutyl polyamine, a Mannich adduct of
polyiso-
butylphenols, aldehyds and monoamines or a Mannich adduct of
polyisobutylphenols,
aldehyds and polyamines or a mixture of the aforementioned dispersant types in
com-
bination with (C) a low-molecular weight polyisobutyl monoamine.
Furthermore, in the fuel additive composition of the instant invention,
dispersant com-
ponent (A) can be a polyisobutyl monoamine, a polyisobutyl polyamine, a
Mannich ad-
duct of polyisobutylphenols, aldehyds and monoamines or a Mannich adduct of
poly-
isobutylphenols, aldehyds and polyamines or a mixture of the aforementioned
dispers-
ant types in combination with (C) a low-molecular weight polyisobutyl
polyamine.
Furthermore, in the fuel additive composition of the instant invention,
dispersant com-
ponent (A) can be a polyisobutyl monoamine, a polyisobutyl polyamine, a
Mannich ad-
duct of polyisobutylphenols, aldehyds and monoamines or a Mannich adduct of
poly-
isobutylphenols, aldehyds and polyamines or a mixture of the aforementioned
dispers-
ant types in combination with (C) a Mannich adduct of a low-molecular weight
polyiso-
butylphenol, an aldehyd and a monoamine.
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18
Furthermore, in the fuel additive composition of the instant invention,
dispersant com-
ponent (A) can be a polyisobutyl monoamine, a polyisobutyl polyamine, a
Mannich ad-
duct of polyisobutylphenols, aldehyds and monoamines or a Mannich adduct of
poly-
isobutylphenols, aldehyds and polyamines or a mixture of the aforementioned
dispers-
ant types in combination with (C) a Mannich adduct of a low-molecular weight
polyiso-
butylphenol, an aldehyd and a polyamine.
In a preferred embodiment, dispersant component (A) and detergent booster
compo-
nent (C) comprise solely polyisobutyl monoamine or polyisobutyl polyamine
species
with the same monoamine or polyamine end groups. The said end group is
preferably
the NH2 group derived from ammonia.
In case of the same amine end groups for the polyisobutyl amines, dispersant
compo-
nent (A) and detergent booster component (C) typically form a mixture of
homologue
polyisobutyl amines exhibiting a bimodal molecular weight distribution. The
same is
true for a mixture of Mannich adducts with the same methyleneamino end groups
both
for components (A) and (C) based on homologue polyisobutylphenols. A bimodal
mo-
lecular weight distribution is normally characterized for organic polymers by
an asym-
metric graph (peak) in the fraction versus molecular weight plot from an
analytical
method like gel permeation chromatography ("GPC"), as used for determination
of the
instant MN values. Small differences in molecular weight result in a shoulder
of the
peak; with growing differences the shoulder forms a second peak. The said
situation
could also be described in mathematical terms as follows: the first deviation
of the
graph exhibits two maxima, whereas the first deviation of a monomodal graph
only ex-
hibits one maximum and one minimum. In case of bimodal molecular weight
distribu-
tion, components (A) and (C) can be produced from the same polymerization and
sub-
sequent amination reaction of isobutene or by the same production of
polyisobutylphe-
nols from isobutene, respectively, with or without separation of the two
species differing
in number average molecular weight e.g. by means of chromatography or
fractional
distillation; the said separation can be done before or after the amination
step or the
Mannich addition reaction, respectively. Alternatively, components (A) and (C)
can be
produced separately and only mixed thereafter together with component (B).
The fuel additive composition
The instant fuel additive composition may be formulated as a concentrate,
using an
inert stable oleophilic (i.e., dissolves in fuel) organic solvent boiling in
the range of
about 65 C to 205 C. Preferably, an aliphatic or an aromatic hydrocarbon
solvent is
used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic
thin-
ners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol,
isobutylcar-
binol, n-butanol, 2-ethylhexanol, and the like, in combination with
hydrocarbon sol-
vents, are also suitable for use in such concentrate. In the concentrate, the
amount of
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19
the instant fuel additive composition will be ordinarily at least 10% by
weight to about
90% by weight, as for example 40 to 85 weight percent or 50 to 80 weight
percent.
In gasoline fuels, other fuel additives may be employed with the additives of
the pre-
sent invention, including, for example, oxygenates, such as tert.-butyl methyl
ether,
antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and
other
dispersants/detergents, such as various hydrocarbyl amines, succinimides or
poly-
etheramines, i.e. hydrocarbyl poly(oxyalkylene) amines. A list of suitable
other dispers-
ant/detergent additives is for example given in WO 00/47698 or in EP-A 1 155
102.
Also included may be lead scavengers, such as aryl halides, e.g.,
dichlorobenzene, or
alkyl halides, e.g., ethylene dibromide. In addition, antioxidants, metal
deactivators,
pour point depressants, corrosion inhibitors and demulsifiers may be present.
In an especially preferred embodiment, the weight ratio of dispersant
component (A) to
dispersant booster component (C) is in the range of from 0.1 : 1 to 10 : 1,
especially of
from 0.3 : 1 to 7 : 1, thus provided the best improvement of intake valve
clean-up per-
formance of gasoline fuels.
An interaction between all three components (A), (B) and (C) is necessary to
achieve
the desired improvement in intake valve clean-up performance. In the instant
fuel addi-
tive composition, the dispersant booster component (C) may exhibit a
synergistic effect
in this respect when used in combination with components (A) and (B) of the
instant
fuel additive composition.
The fuel composition
The fuel additive composition of the present invention will generally be
employed in a
liquid hydrocarbon distillate fuel boiling in the gasoline range. It is in
principle suitable
for use in all types of gasoline, including "light" and "severe" gasoline
species. The
gasoline fuels may also contain amounts of other fuel components such as, for
exam-
ple, ethanol.
The proper concentration of the instant fuel additive composition necessary in
order to
achieve the desired intake valve clean-up performance varies depending upon
the type
of fuel employed, and may also be influenced by the presence of other
detergents, dis-
persants and other additives, etc. Generally, however, from 80 to 8000 weight
ppm,
especially from 180 to 2600 weight ppm, of the instant fuel additive
composition per
part of base fuel is needed to achieve the best results.
In an especially preferred embodiment, dispersant component (A) is present in
the in-
stant fuel composition at a level of from more than 20 to 3000 ppm, especially
from 70
to 800 ppm, carrier oil component (B) at a level of from 50 to 2000 ppm,
especially from
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WO 2011/151207 PCT/EP2011/058313
100 to 600 ppm, and amine component (C) at a level of from 10 to 3000 ppm,
espe-
cially from 30 to 1200 ppm (all ppm values refer to the weight).
Typically, gasoline fuels, which may be used according to the present
invention exhibit,
5 in addition, one or more of the following features:
The aromatics content of the gasoline is preferably not more than 50 volume %
and
more preferably not more than 45 volume %. Preferred ranges for the aromatics
con-
tent are from 1 to 45 volume % and particularly from 5 to 40 volume %.
The sulfur content of the gasoline is preferably not more than 100 ppm by
weight and
more preferably not more than 50 ppm by weight. Preferred ranges for the
sulfur con-
tent are from 0.5 to 150 ppm by weight and particularly from 1 to 100 ppm by
weight.
The gasoline has an olefin content of not more than 21 volume %, preferably
not more
than 18 volume %, and more preferably not more than 10 volume %. Preferred
ranges
for the olefin content are from 0.1 to 21 volume % and particularly from 2 to
18 volume
%.
The gasoline has a benzene content of not more than 1.0 volume % and
preferably not
more than 0.9 volume %. Preferred ranges for the benzene content are from 0 to
1.0 volume % and preferably from 0.05 to 0.9 volume %.
The gasoline has an oxygen content of not more than 45 weight %, preferably
from 0 to
45 weight %, and most preferably from 0.1 to 2.7 weight % (first type) or most
prefera-
bly from 2.7 to 45 weight % (second type). The gasoline of the second type
mentioned
above is a mixture of lower alcohols such as methanol or especially ethanol,
which
derive preferably from natural source like plants, with mineral oil based
gasoline, i.e.
usual gasoline produced from crude oil. An example for such gasoline is "E
85", a mix-
ture of 85 volume % of ethanol with 15 volume % of mineral oil based gasoline.
The content of alcohols, especially lower alcohols, and ethers in a gasoline
of the first
type mentioned in the above paragraph is normally relatively low. Typical
maximum
contents are for methanol 3 volume %, for ethanol 5 volume %, for isopropanol
10 volume %, for tert.-butanol 7 volume %, for isobutanol 10 volume %, and for
ethers
containing 5 or more carbon atoms in the molecule 15 volume %.
For example, a gasoline which has an aromatics content of not more than 38
volume %
and at the same time an olefin content of not more than 21 volume %, a sulfur
content
of not more than 50 ppm by weight, a benzene content of not more than 1.0
volume %
and an oxygen content of from 0.1 to 2.7 weight % may be applied.
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The summer vapor pressure of the gasoline is usually not more than 70 kPa and
pref-
erably not more than 60 kPa (at 37 C).
The research octane number ("RON") of the gasoline is usually from 90 to 100.
A usual
range for the corresponding motor octane number ("MON") is from 80 to 90.
The above characteristics are determined by conventional methods (DIN EN 228).
The internal combustion engine
The above dispersant booster component (C) is preferably used as an intake
valve
clean-up booster in accordance with the instant invention in gasoline-operated
port fuel
injection internal combustion engines which are different in view of their
construction
and their mode of operation from direct injection spark ignition engines.
Experimental Part
The following examples are presented to illustrate specific embodiments of
this inven-
tion and are not to be construed in any way as limiting the scope of the
invention.
Examples 1 and 2: Determination of intake valve deposits ("IVD")
Intake valve deposits were determined in gasoline-operated internal combustion
en-
gines of the Mercedes Benz M 102E type according to test procedure CEC F-05-A-
93
(Examples 1 a and 1 b) and of the Mercedes Benz M 111 type according to test
proce-
dure CEC F-20-A-98 (Examples 2a and 2b). A usual Eurosuper gasoline according
to
EN 228 was used as the base fuel. The deposits on the four valves of the
engines were
determined and the average thereof value was calculated.
The following additives were used:
Al: polyisobutyl monoamine based on highly reactive polyisobutene with a
methylvi-
nylidene content of 80 mole-% and MN = 1000 subjected to hydroformylation and
subsequent reductive amination with ammonia
B1: polyether carrier oil obtained from tridecanol and 22 moles of butylene
oxide
Cl: polyisobutyl monoamine based on highly reactive polyisobutene with a
methylvi-
nylidene content of 80 mole-% and MN = 420 subjected to hydroformylation and
subsequent reductive amination with ammonia
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Example 1 a (for comparision):
A Mercedes Benz M 102E engine was run according to CEC F-05-A-93 for 60 hours
with an Eurosuper gasoline fuel containing 300 wt.-ppm of Al and 75 wt.-ppm of
B1.
As a result, the following IVD values were obtained: 12 mg, 20 mg, 67 mg, 8
mg; aver-
age: 21 mg. Running the same test without any additives resulted in an average
IVD
value of 153 mg.
Example 1 b (according to the instant invention):
The same Mercedes Benz M 102E engine was run according to CEC F-05-A-93 for 60
hours with an Eurosuper gasoline fuel containing 300 wt.-ppm of Al, 75 wt.-ppm
of B1
and 50 mg of C1. As a result, the following IVD values were obtained: 3 mg, 0
mg, 12
mg, 10 mg; average: 6 mg.
Example 2a (for comparision):
A Mercedes Benz M 111 engine was run according to CEC F-20-A-98 for 60 hours
with an Eurosuper gasoline fuel containing 400 wt.-ppm of Al and 100 wt.-ppm
of B1.
As a result, the following IVD values were obtained (double determination):
143/175
mg, 73/164 mg, 55/68 mg, 156/148 mg; average: 123 mg. Running the same test
with-
out any additives resulted in an average IVD value of 359 mg.
Example 2b (according to the instant invention):
The same Mercedes Benz M 111 engine was run according to CEC F-20-A-98 for 60
hours with an Eurosuper gasoline fuel containing 300 wt.-ppm of Al, 75 wt.-ppm
of B1
and 50 mg of C1. As a result, the following IVD values were obtained: 80/87
mg, 46/42
mg, 73/48 mg, 125/135 mg; average: 80 mg.
