Note: Descriptions are shown in the official language in which they were submitted.
CA 02549647 2006-06-14
Fuel and lubricant additive concentrates comprising at least one anthraquinone
derivative as a marker
Description
The present invention relates to fuel and lubricant additive concentrates
which
comprise at least one anthraquinone derivative as a marker, to the use of such
concentrates for additizing mineral oils, and also to mineral oils which
comprise such
concentrates.
For mineral oil additization, additive concentrates (also referred to herein
below,
following the relevant terminology, as packages) are used which, in addition
to a carrier
oil and a mixture of different fuel additives, generally also comprise dyes
and also, for
invisible fiscal or manufacturer-specific marking, additionally markers. These
packages
enable the supply of different mineral oil distributors from a pool of
unadditized mineral
oil, to which the company-specific additization, color and marker are imparted
only, for
example, while the mineral oil is being filled into appropriate transport
containers, with
the aid of their individual packages.
The markers are usually substances which are either extracted from the mineral
oil and
subsequently converted to colored compounds by derivatization, or substances
which
exhibit absorption either in the visible or in the invisible wavelength region
of the
spectrum (for example in the NIR). Markers which have been proposed and find
use
per se, i.e. not just after preceding derivatization, include highly differing
compound
classes, for example phthalocyanines, naphthalocyanines, nickel-dithiolene
complexes,
aminium compounds of aromatic amines, methine dyes and azulenesquaric acid
dyes
(for example WO 94/02570 A1, WO 96/10620 A1 ), but also bisazo dyes (for
example
EP 256 460 A1). Anthraquinone derivatives for coloring gasoline or mineral
oils are
described in the documents US 2,611,772, US 2,068,372, EP 1 001 003 A1 and
EP 1 323 811 A2.
Experience has shown that many of the current markers are stable under the
dilute
conditions in the mineral oil, but not under the concentrated conditions in
the packages;
the action of the package components changes the characteristics (e.g.
extinction) of
the markers within a very short time.
It is thus an object of the present invention to provide fuel and lubricant
additive
concentrates which feature very good long-term storage stability, especially
also with
regard to the stability of the markers present therein against the action of
the remaining
components of these concentrates.
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Accordingly, the fuel and lubricant additive concentrates (packages) mentioned
at the
outset have been found, which comprise at least one anthraquinone derivative
as a
marker.
The components of the inventive packages are in particular:
a) at least one anthraquinone derivative,
b) at least one carrier oil,
c) at least one additive selected from the group consisting of
detergents,
dispersants and
valve seat wear-inhibiting additives,
d) and also, if appropriate, further additives and assistants.
The component a) used is in particular anthraquinone derivatives which are
selected
from the group consisting of the compounds
of the formula I
0
R
/
of the formula II
O HN~R'
X m
/ /
O HN~RZ
and of the formula III
iii
Rs
R5
R.
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3
where
Z', Z2 are each independently hydrogen, hydroxyl, OR, NHR or NR2,
R', R2 are each independently R or COR,
X is hydrogen, cyano, nitro, hydroxyl, OR, amino, NHR, R or
CH(R9)(R'°),
n, m are each 0, 1, 2, 3 or 4, and, in each case that n or m is greater than
1, the
R or X radicals may each be the same or different,
R9, R'° are each independently cyano, COOH or COOR,
R3 is hydrogen, R or NHR,
R4 to RS are each independently hydrogen, R or NHR
and
R is C,-C2o-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms
in
ether function, C5-C~-cycloalkyl which is optionally substituted by one or
more C~-C2o-alkyl groups which are optionally interrupted by from 1 to 4
oxygen atoms in ether function, saturated heterocyclic five- or six-
membered radical which is optionally substituted by one or more C,-C2o-
alkyl groups which are optionally interrupted by from 1 to 4 oxygen atoms in
ether function, or is C6-C,o-aryl which is optionally substituted by one or
more halogen, cyano, nitro, hydroxyl, amino, C,-C2o-alkyl which is optionally
interrupted by from 1 to 4 oxygen atoms in ether function, C,-CZO-alkoxy, C,-
CZO-alkylamino or C,-C2o-dialkylamino, or is heteroaryl having from 3 to 12
carbon atoms which is optionally substituted by one or more C~-C2o-alkyl
which is optionally interrupted by from 1 to 4 oxygen atoms in ether
function, C,-C2o-alkoxy, C,-C2o-alkylamino or C,-C2o-dialkylamino, or is C6-
C~o-aryl-C,-C4-alkyl which is optionally substituted in the aryl radical by
one
or more halogen, cyano, nitro, hydroxyl, amino, C,-C2o-alkyl which is
optionally interrupted by from 1 to 4 oxygen atoms in ether function, C~-CZO-
alkoxy, C~-C2o-alkylamino or C,-C2o-dialkylamino, or is heteroaryl-C,-C4-
alkyl having from 3 to 12 carbon atoms in the heteroaryl radical, the latter
optionally being substituted by one or more C,-C2°-alkyl which is
optionally
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4
interrupted by from 1 to 4 oxygen atoms in ether function, C~-CZ°-
alkoxy, C,-
C2°-alkylamino or C,-C2°-dialkylamino.
C~-C2°-Alkyl which is optionally interrupted by from 1 to 4 oxygen
atoms in ether
function include, for example, methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl,
tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl,
heptyl, hept-3-
yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl,
dodecyl,
tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above terms isooctyl,
isononyl,
isodecyl and isotridecyl are trivial names and stem from the alcohols obtained
by the
oxo process - on this subject, cf. Ullmanns Encyklopadie der technischen
Chemie, 4th
Edition, Volume 7, pages 215 to 217, and also Volume 11, pages 435 and 436),
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-
propoxyethyl,
2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl,
2- or 3-
propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-
ethoxybutyl, 2- or 4-
propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-
dioxanonyl, 3,7-
dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl,
3,6,8-
trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl or 3,6,9,12-
tetraoxatetradecyl.
Useful C5-C~-cycloalkyl radicals include cyclopentyl, cyclohexyl and
cycloheptyl. These
cycloalkyls are optionally substituted by one or more, in particular up to
three, C,-CZ°-
alkyl groups, and the latter may optionally be interrupted by from 1 to 4
oxygen atoms
in ether function. Examples of such C~-C2°-alkyl groups optionally
interrupted by
oxygen atoms have already been listed above.
Saturated, heterocyclic five- or six-membered radicals which are optionally
substituted
by one or more C,-CZ°-alkyl groups which are optionally interrupted by
from 1 to 4
oxygen atoms in ether function are derived, for example, from pyrrolidine, 2-
or 3-
methylpyrrolidine, 2,4-dimethyl-3-ethylpyrrolidine, pyrazolidine, 2-, 3-, 4-
or 5-
methylpyrazolidine, imidazolidine, 2-, 3-, 4- or 5-methylimidazolidine,
oxazolidine, 2-, 4-
or 5-methyloxazolidine, isoxazolidine, 3-, 4- or 5-methylisoxazolidine,
piperidine, 2-, 3-,
4-methyl- or -ethylpiperidine, 2,6-dimethylpiperidine, piperazine, 4-(C,-C4-
alkyl)piperazine such as 4-methyl- or 4-ethylpiperazine, morpholine,
thiomorpholine or
thiomorpholine S,S-dioxide.
When R, in the OR, NHR and NR2 groups of the definition of the variables Z'
and/or Z2,
in the OR and NHR groups of the definition of the variables X, in the COOR
group of
the definition of the R9 and R'° radicals, in the NHR group of the
definition of the
variables R3 and also R4 to R8, corresponds to an appropriate, optionally
substituted,
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1
w
saturated, heterocyclic five- or six-membered radical, it is bonded to the
particular
heteroatom of the group in question via a carbon atom of the heterocyclic five-
or six-
membered ring. The same applies when R alone in the definition of the
variables R'
and R2 and the definition of the variables R3 corresponds to an appropriate,
optionally
substituted, saturated, heterocyclic five- or six-membered radical. In the
other cases,
the bonding may either be via a carbon atom or a heteroatom of the
heterocyclic five-
or six-membered radical which are suitable for bonding.
C6-C,o-Aryls include in particular phenyl and naphthyl. These are optionally
substituted
by one or more halogen such as fluorine, chlorine or bromine, cyano, nitro,
hydroxyl,
amino, C~-C2o-alkyl which is optionally interrupted by from 1 to 4 oxygen
atoms in ether
function, C,-CZO-alkoxy, C,-CZO-alkylamino or C,-C2o-dialkylamino. Appropriate
C~-CZO-
alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in
ether
function, and C,-CZO-alkyl radicals which are present in the C,-C2o-alkoxy, C,-
C2°-
alkylamino or C,-C2o-dialkylamino groups have already been listed above by way
of
example.
Heteroaryl radicals having from 3 to 12 carbon atoms which are optionally
substituted
by one or more C~-C2o-alkyl which is optionally interrupted by from 1 to 4
oxygen atoms
in ether function, C~-CZO-alkoxy, C,-C2o-alkylamino or C,-C2o-dialkylamino are
derived,
for example, from pyrrole, furan, thiophene, pyrazole, isoxazole, isothiazole,
imidazole,
1 H-1,2,3-triazole, 1 H-1,2,4-triazole, pyridine, pyrazine, pyridazine, 1 H-
azepine, 2H-
azepine, oxazole, thiazole, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4-
or 1,3,4-
thiadiazole and also optionally the benzo or dibenzofused rings, for example
quinoline,
isoquinoline, indole, benzo[b]furan (coumarone), benzo(b]thiophene
(thionaphthene),
carbazole, dibenzofuran, dibenzothiophene, 1 H-indazole, indoxazole,
benzo[d]isothiazole, anthranil, benzimidazole, benzoxazole, benzothiazole,
cinnoline,
phthalazine, quinazoline, quinoxaline or phenazine. C~-C2o-Alkyl substituents
which are
optionally interrupted by from 1 to 4 oxygen atoms in ether function have
already been
specified above by way of example.
When R, in the OR, NHR and NRZ groups of the definition of the variables Z'
and/or Z2,
in the OR and NHR groups of the definition of the variables X, in the COOR
group of
the definition of the R9 and R'° radicals, in the NHR group of the
definition of the
variables R3 and also R4 to Re, corresponds to an appropriate, optionally
substituted
heteroaryl, it is bonded to the particular heteroatom of the group in question
via a
carbon atom of the heteroaryl. The same applies when R alone in the definition
of the
variables R' and/or R2 and the definition of the variables R3 corresponds to
an
appropriate, optionally substituted heteroaryl. In the other cases, the
bonding may
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s
either be via a carbon atom or a heteroatom of the heteroaryl which is
suitable for
bonding.
C6-C,°-Aryl-C,-C4-alkyls which are optionally substituted in the aryl
radical by one or
more halogen, cyano, nitro, hydroxyl, amino, C,-C2°-alkyl which is
optionally interrupted
by from 1 to 4 oxygen atoms in ether function, C,-C2°-alkoxy, C,-
CZ°-alkylamino or C,-
C2°-dialkylamino include in particular benzyl, phenylethyl, 3-
phenylpropyl and 4-
phenylbutyl. Appropriate C,-C2°-alkyl radicals which are optionally
interrupted by from 1
to 4 oxygen atoms in ether function, and C,-CZ°-alkyl radicals which
are present in the
C,-C2°-alkoxy, C,-C2°-alkylamino or C,-CZ°-dialkylamino
groups have already been
listed above by way of example.
Heteroaryl-C,-C4-alkyls having from 3 to 12 carbon atoms in the heteroaryl
radical, the
latter optionally being substituted by one or more C,-C2°-alkyl which
is optionally
interrupted by from 1 to 4 oxygen atoms in ether function, C,-C2°-
alkoxy, C,-CZ°-alkyl-
amino or C,-CZ°-dialkylamino are derived, for example, from the
heteroaryl radicals
specified above which are bonded to the C,-C4-alkyl radicals either via a
carbon atom
or a heteroatom of the heteroaryl which is suitable for bonding. Appropriate
C,-CZ°-alkyl
radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether
function,
and C,-Cz°-alkyl radicals which are present in the C,-CZ°-
alkoxy, C,-C2°-alkylamino or
C,-CZ°-dialkylamino groups have already been listed above by way of
example.
Preferred inventive fuel and lubricant additive concentrates comprise
anthraquinone
derivatives of the formulae I, II and III where
Z', Z2 are each independently hydrogen or NHR,
R', RZ are each independently R,
X is hydrogen, cyano or CH(R9)(R'°),
n, m are 0, 1, 2, 3 or 4, and, when n or m is greater than 1, the R or X
radicals are
the same or different,
R9, R'° are each independently cyano or COOR,
R3 is hydrogen, R or NHR,
R4 to R' are hydrogen or NHR,
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7
R8 is NHR
and
R is C~-C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms
in
ether function, cyclohexyl which is optionally substituted by one or more C,-
C,5-alkyl groups which are optionally interrupted by from 1 to 4 oxygen
atoms in ether function, saturated heterocyclic five- or six-membered radical
which is optionally substituted by one or more C,-C,5-alkyl groups which are
optionally interrupted by from 1 to 4 oxygen atoms in ether function, or is
C6-Coo-aryl which is optionally substituted by one or more C,-C,5-alkyl which
is optionally interrupted by from 1 to 4 oxygen atoms in ether function, C~-
C,5-alkoxy, C,-C,5-alkylamino or C,-C,5-dialkylamino, or is heteroaryl having
from 3 to 5 carbon atoms which is optionally substituted by one or more C,-
C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether
function, C,-C,5-alkoxy, C,-C~5-alkylamino or C,-C,5-dialkylamino, or is
phenyl C,-C4-alkyl which is optionally substituted in the phenyl radical by
one
or more C,-C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen
atoms in ether function, C~-C,5-alkoxy, C,-C,5-alkylamino or C,-C,5-
dialkylamino, or is heteroaryl-C,-C4-alkyl having from 3 to 5 carbon atoms in
the heteroaryl radical, the latter optionally being substituted by one or more
C,-C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in
ether function, C,-C,5-alkoxy, C,-C,5-alkylamino or C,-C,5-dialkylamino,
the preferred R radicals already having been listed in the above exemplary
list.
Anthraquinone derivatives of the formula I are in particular the compounds of
the
formulae la to If shown below:
0 0 0
R I \ I \ R I \ I \ R I \ I \ R
/ / / / / /
R R R R R
O O O
> >
(la) (Ib) (Ic)
0 0 0
I \ I \ I \ I \ R I \ I \
/ / / / / /
R R R R
o , o and o
(Id) (le) (If)
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In the formulae la to le, the variables R are in each case independently, and
in formula
If the variable R is, C,-C,5-alkyl which is optionally interrupted by from 1
to 4 oxygen
atoms in ether function, and C6-C,o-aryl which is optionally substituted by
one or more
C,-C,5-alkyl whch is optionally interrupted by from 1 to 4 oxygen atoms in
ether
function.
In the definition of a C,-C~5-alkyl which is optionally substituted by from 1
to 4 oxygen
atoms in ether function, the variables R are preferably selected from the
group
consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
tert-butyl, pentyl,
isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl,
octyl, 2-
ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,
tridecyl, 3,5,5,7-
tetramethylnonyl, isotridecyl, tetradecyl, pentadecyl, methoxymethyl, 2-
ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-
isopropoxyethyl,
2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-
propoxypropyl,
2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-
propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-
dioxanonyl,
3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-
dioxadecyl, 3,6,8-
trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-
tetraoxatetradecyl.
In the definition of a Cs-Coo-aryl which is optionally substituted by one or
more C,-C,5-
alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether
function, the
variables R are preferably selected from the group consisting of unsubstituted
phenyl,
the 2-, 3- and 4-monosubstituted, the 2,3-, 2,4- and 3,4-disubstituted and the
2,3,4-,
2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trisubstituted phenyl radicals which
are
substituted by the C,-C,5-alkyl radicals which are optionally interrupted by
oxygen in
ether function and have been listed above by way of example.
The particular R radicals in the compounds of the formulae la to le are
preferably the
same.
Anthraquinone derivatives of the formula II are in particular the compounds of
the
formulae Ila to Ilc shown below:
R~NH O HN~R O HN~R O HN~R
\ \ X I \ \ X I \ \ X
/ / 2 / / z / /
R~NH O HN~Rz R~NH O HN~RZ O HN~RZ
(Ila) (Ilb) (Ilc)
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9
In the formulae Ila to Ilc, the variables R, R' and R2 are each independently
C,-C,5-
alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether
function, and
Cs-C,°-aryl which is optionally substituted by one or more C,-C,5-alkyl
which is
optionally interrupted by from 1 to 4 oxygen atoms in ether function.
X in the formulae Ila to Ilc either takes the meaning of two hydrogen atoms,
two cyano
groups in the 2,3- or 6,7-arrangement or two identical CH(R9)(R'°)
groups in the 2,3- or
6,7-arrangement of the anthraquinone structure. The latter two
CH(R9)(R'°) groups are
either two CH(COOR)2, CH(CN)COOR or CH(CN)2 groups, where the R radicals are
preferably C,-C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen
atoms in
ether function, or C6-C,°-aryl which is optionally substituted by one
or more C,-C,5-alkyl
which is optionally interrupted by from 1 to 4 oxygen atoms in ether function.
In the definition of a C,-C,5-alkyl which is optionally interrupted by from 1
to 4 oxygen
atoms in ether function, the variables R, R' and RZ are preferably selected
from the
group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-
butyl, tert-butyl,
pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-
3-yl, octyl,
2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,
tridecyl,
3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, pentadecyl, methoxymethyl,
2-
ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-
isopropoxyethyl,
2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-
propoxypropyl,
2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-
propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-
dioxanonyl,
3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-
dioxadecyl, 3,6,8-
trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-
tetraoxatetradecyl.
In the definition of a Cs-C,°-aryl which is optionally substituted by
one or more C,-C,5-
alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether
function, the
variables R, R' and RZ are preferably selected from the group consisting of
unsubstituted phenyl, the 2-, 3- and 4-monosubstituted, 2,3-, 2,4- and 3,4-
disubstituted
and the 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trisubstituted phenyl
radicals
which are substituted by the C,-C,5-alkyl radicals which are optionally
interrupted by
oxygen in ether function and are listed above by way of example.
Particular preference is given to compounds of the formulae Ila, Ilb and Ilc
in which
both variables R, R' and RZ, or R, R' and Rz, or R' and R2 are the same as one
another, i.e. corresponding compounds include:
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R~NH O HN~R R~NH O HN~R O HN~R
\ ~ \ CN I \ I \ ~ \ I \ CN
/ / CN / / / / CN
R~NH O HN~R R~NH O HN~R R~NH 0 HN~R
, ,
O HN~R O HN~R O HN~R
\ ~ \ ~ \ ~ \ CN ~ \ ~ \
/ / / / CN / /
R~NH O HN~R O HN~R O HN~R
R~NH O HN~R O HN~R
\ CH(R9)(R,o) ~ \ I \ CH(R9)(R,o)
/ CH(R9)(R~o) / / CH(R9)(R,o)
R~NH O HN~R R~NH O HN~R
5
and
O HN~R
CH(R9)(Rio)
\ ~ \
/ CH(R9)(R~o)
O HN~R
and also the corresponding compounds 6,7-substituted by cyano groups or
10 CH(R9)(R'°) groups, the variables R corresponding to the selections
listed above.
Anthraquinone derivatives of the formula III to be used in accordance with the
invention
are in particular the compounds of the formulae Illa to Illd shown below:
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11
(Illa)
(Illb)
Wo Wi
(IIIC) (IIId) K
where
R3 is R or NHR,
R8 is NHR
W is R4 to R' radicals in the definition of hydrogen or NHR,
p is 1, 2, 3 or 4, and, when p is greater than 1, the radicals are the same,
and
R is C,-C,5-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms
in
ether function, cyclohexyl which is optionally substituted by one or more C,-
C,5-
alkyl groups which are optionally interrupted by from 1 to 4 oxygen atoms in
ether function, saturated heterocyclic five- or six-membered radical which is
optionally substituted by one or more C,-C,5-alkyl groups which are optionally
interrupted by from 1 to 4 oxygen atoms in ether function, or is C6-C,o-aryl
which
is optionally substituted by one or more C~-C~5-alkyl which is optionally
interrupted by from 1 to 4 oxygen atoms in ether function, C,-C~5-alkoxy, C~-
C~5-
alkylamino or C,-C,5-dialkylamino, or is heteroaryl having from 3 to 5 carbon
atoms which is optionally substituted by one or more C,-C,5-alkyl which is
optionally interrupted by from 1 to 4 oxygen atoms in ether function, C,-C,5-
CA 02549647 2006-06-14
,, 12
alkoxy, C,-C,5-alkylamino or C,-C~5-dialkylamino, or is phenyl C,-C4-alkyl
which
is optionally substituted in the phenyl radical by one or more C,-C,5-alkyl
which is
optionally interrupted by from 1 to 4 oxygen atoms in ether function, C~-C~5-
alkoxy, C,-C,5-alkylamino or C~-C,5-dialkylamino, or is heteroaryl-C,-C4-alkyl
having from 3 to 5 carbon atoms in the heteroaryl radical, the latter
optionally
being substituted by one or more C,-C~5-alkyl which is optionally interrupted
by
from 1 to 4 oxygen atoms in ether function, C,-C,5-alkoxy, C,-C,5-alkylamino
or
C,-C,5-dialkylamino,
the preferred R radicals already having been listed by way of example in the
above-
described general definition of the R radicals.
R in the formulae Illa to Illd is more preferably C,-C~5-alkyl which is
optionally
interrupted by from 1 to 4 oxygen atoms in ether function, or C6-C,o-aryl
which is
optionally interrupted by one or more C,-C,5-alkyl which is optionally
interrupted by
from 1 to 4 oxygen atoms in ether function.
In particular, R in the formulae Illa to Illd is selected from the group
consisting of
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
pentyl, isopentyl,
neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-
ethylhexyl,
isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl,
3,5,5,7-
tetramethylnonyl, isotridecyl ,tetradecyl, pentadecyl, methoxymethyl, 2-
ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-
isopropoxyethyl,
2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-
propoxypropyl,
2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-
propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-
dioxanonyl,
3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-
dioxadecyl, 3,6,8-
trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-
tetraoxatetradecyl,
unsubstituted phenyl, the 2-, 3- and 4-monosubstituted, the 2,3-, 2,4- and 3,4-
disubstituted and the 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-
trisubstituted phenyl
radicals which are substituted by the C~-C~5-alkyl radicals which are
optionally
interrupted by oxygen in ether function and have been listed above by way of
example,
selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl,
isobutyl,
sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-
methylpentyl,
heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl,
isodecyl, undecyl,
dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl,
pentadecyl,
methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-
propoxyethyl,
2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-
ethoxypropyl, 2-
and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-
ethoxybutyl, 2- and 4-propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-
CA 02549647 2006-06-14
s
dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,
4,7-
dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-
tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl.
The carrier oils used are typically viscous, high-boiling and in particular
thermally stable
liquids. They cover the hot metal surfaces, for example the intake valves,
with a thin
liquid film and thus prevent or delay the formation and deposition of
decomposition
products on the metal surfaces.
Carrier oils useful as component b) of the inventive fuel and lubricant
additive
concentrates are, for example, mineral carrier oils (base oils), especially
those of the
Solvent Neutral (SN) 500 to 2000 viscosity class, synthetic carrier oils based
on olefin
polymers having MN = from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or nonhydrogenated), on poly-alpha-olefins or
poly(internal olefins) and also synthetic carrier oils based on alkoxylated
long-chain
alcohols or phenols. According to the invention, adducts, to be used as
carrier oils, of
ethylene oxide, propylene oxide and/or butylene oxide to polybutyl alcohols or
polyisobutene alcohols are described for instance, in EP 277 345 A1; further
polyalkene alcohol polyalkoxylates to be used in accordance with the invention
are
described in WO 00/50543 A1. Further carrier oils to be used in accordance
with the
invention also include polyalkene alcohol polyether amines, as detailed in
WO 00/61708.
It will be appreciated that mixtures of different carrier oils may also be
used, as long as
they are compatible with one another and with the remaining components of the
inventive packages.
Carburetors and intake systems of internal combustion engines, but also
injection
systems for fuel metering, are being contaminated to an increasing degree by
impurities which are caused, for example, by dust particles from the air and
uncombusted hydrocarbons from the combustion chamber.
To reduce or prevent these contaminations, additives ("detergents") are added
to the
fuel to keep valves and carburetors or injection systems clean. Such
detergents are
generally used in combination with one or more carrier oils. The carrier oils
exert an
additional "wash function", support and often promote the detergents in their
action of
cleaning and keeping clean, and can thus contribute to the reduction in the
amount of
detergents required.
CA 02549647 2006-06-14
_"
14
It should also be mentioned here that many of the substances typically used as
carrier
oils display additional action as detergents and/or dispersants, which is why
the
proportion of the latter can be reduced in such a case. Such carrier oils
having
detergent/dispersant action are detailed, for instance, in the last-mentioned
WO
document.
It is also often impossible to clearly delimit the mode of action of
detergents,
dispersants and valve seat wear-inhibiting additives, which is why these
compounds
are listed in summary under component c). Customary detergents which find use
in the
inventive packages are listed, for example, in WO 00/50543 A1 and WO 00/61708
A1
and include:
Polyisobutenamines which are obtainable according to EP-A 244 616 by
hydroformylation of highly reactive polyisobutene and subsequent reductive
amination with ammonia, monoamines or polyamines, such as
dimethylenaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or tetraethylenepentamine,
Poly(iso)butenamines which are obtainable by chlorination of polybutenes or
polyisobutenes having double bonds predominantly in the b- and g-position and
subsequent amination with ammonia, monoamines or the abovementioned
polyamines,
Poly(iso)butenamines which are obtainable by oxidation of double bonds in
poly(iso)butenes with air or ozone to give carbonyl or carboxyl compounds and
subsequent amination under reducing (hydrogenating) conditions,
Polyisobutenamines which are obtainable according to DE-A 196 20 262 from
polyisobutene epoxides by reaction with amines and subsequent dehydration and
reduction of the amino alcohols,
Polyisobutenamines which optionally contain hydroxyl groups and are obtainable
according to WO-A 97/03946 by reaction of polyisobutenes having an average
degree of polymerization P of from 5 to 100 with oxides of nitrogen or
mixtures of
oxides of nitrogen and oxygen and subsequent hydrogenation of these reaction
products,
Hydroxyl-containing polyisobutenamines which are obtainable according to EP-A
476 485 by reaction of polyisobutene epoxides with ammonia, monoamines or
the abovementioned polyamines,
CA 02549647 2006-06-14
Polyetheramines which are obtainable by reaction of CZ- to C3o-alkanols, C6-
to
C3o-alkanediols, mono- or di-C2- to C3o-alkylamines, C,- to C3o-
alkylcyclohexanols
or C,- to C3o-alkylphenols with from 1 to 30 mol of ethylene oxide and/or
5 propylene oxide and/or butylene oxide per hydroxyl or amino group and
subsequent reductive amination with ammonia, monoamines or the
abovementioned polyamines, and also
"Polyisobutene Mannich bases" which are obtainable according to EP-A 831 141
10 by reaction of polyisobutene-substituted phenols with aldehydes and
monoamines or the abovementioned polyamines.
Further detergents and/or valve seat wear-inhibiting additives to be used in
accordance
with the invention are listed, for example, in WO 00/47698 A1 and include
compounds
15 which have at least one hydrophobic hydrocarbon radical having a number-
average
molecular weight (MN) of from 85 to 20 000 and at least one polar moiety, and
which
are selected from:
(i) mono- or polyamino groups having up to 6 nitrogen atoms, of which at least
one
nitrogen atom has basic properties;
(ii) nitro groups, optionally in combination with hydroxyl groups;
(iii) hydroxyl groups in combination with mono- or polyamino groups, in which
at least
one nitrogen atom has basic properties;
(iv) carboxyl groups or their alkali metal or their alkaline earth metal
salts;
(v) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(vi) polyoxy-C2- to -C4-alkylene groups which are terminated by hydroxyl
groups,
mono- or polyamino groups, in which at least one nitrogen atom has basic
properties, or by carbamate groups;
(vii) carboxylic ester groups;
CA 02549647 2006-06-14
16
(viii) moieties derived from succinic anhydride and having hydroxyl and/or
amino
and/or amido and/or imido groups; and/or
(ix) moieties obtained by Mannich reaction of substituted phenols with
aldehydes and
mono- or polyamines.
Additives containing mono- or polyamino groups (i) are preferably
polyalkenemono- or
polyalkenepolyamines based on polypropene or on highly reactive (i.e. having
predominantly terminal double bonds, usually in the ~3- and y-positions) or
conventional
(i.e. having predominantly internal double bonds) polybutene or polyisobutene
having
MN = from 300 to 5000. Such additives based on highly reactive polyisobutene,
which
can be prepared from the polyisobutene (which may contain up to 20% by weight
of n-
butene units) by hydroformylation and reductive amination with ammonia,
monoamines
or polyamines, such as dimethylaminopropylamine, ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are
disclosed in
particular in EP 244 616 A2. When polybutene or polyisobutene having
predominantly
internal double bonds (usually in the Vii- and y-positions) are used as
starting materials
in the preparation of the additives, a possible preparative route is by
chlorination and
subsequent amination or by oxidation of the double bond with air or ozone to
give the
carbonyl or carboxyl compound and subsequent amination under reductive
(hydrogenating) conditions. The amines used here for the amination may be the
same
as those used above for the reductive amination of the hydroformylated highly
reactive
polyisobutene. Corresponding additives based on polypropene are described in
particular in WO 94/24231 A1.
Further preferred additives containing monoamino groups (i) are the
hydrogenation
products of the reaction products of polyisobutenes having an average degree
of
polymerization P = from 5 to 100 with nitrogen oxides or mixtures of nitrogen
oxides
and oxygen, as described in particular in WO 97/03946 A1.
Further preferred additives containing monoamino groups (i) 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 196 20 262 A1.
Additives containing vitro groups (ii), optionally in combination with
hydroxyl groups,
are preferably reaction products of polyisobutenes having an average degree of
polymerization P of from 5 to 100 or from 10 to 100 with nitrogen oxides or
mixtures of
nitrogen oxides and oxygen, as described in particular in WO 96/03367 A1 and
CA 02549647 2006-06-14
17
WO 96/03479 A1. These reaction products are generally mixtures of pure
nitropolyisobutanes (e.g. a,~i-dinitropolyisobutane) and mixed
hydroxynitropolyisobutanes (e.g. a-nitro-~3-hydroxypolyisobutane).
Additives containing hydroxyl groups in combination with mono- or polyamino
groups
(iii) are in particular reaction products of polyisobutene epoxides obtainable
from
polyisobutene having preferably predominantly terminal double bonds and MN =
from
300 to 5000, with ammonia or mono- or polyamines, as described in particular
in
EP 476 485 A1.
Additives containing carboxyl groups or their alkali metal or alkaline earth
metal salts
(iv) are preferably copolymers of CZ-C4o-olefins with malefic anhydride which
have a
total molar mass of from 500 to 20 000 and of whose carboxyl groups some or
all 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 307 815 A1. Such additives serve mainly to
prevent valve
seat wear and can, as described in WO 87/01126 A1, advantageously be used in
combination with customary detergents such as poly(iso)butenamines or
polyetheramines.
Additives containing sulfonic acid groups or their alkali metal or alkaline
earth metal
salts (v) are preferably alkali metal or alkaline earth metal salts of an
alkyl
sulfosuccinate, as described in particular in EP 639 632 A1. Such additives
serve
mainly to prevent valve seat wear and can be used advantageously in
combination with
customary detergents such as poly(iso)butenamines or polyetheramines.
Additives containing polyoxy-C2-C4-alkylene moieties (vi) are preferably
polyethers or
polyetheramines which are obtainable by reaction of C2- to Cso-alkanols, C6-
to C3o-
alkanediols, mono- or di-C2-C3o-alkylamines, C~-C3o-alkylcyclohexanols or C,-
C30-
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 310 875 A1,
EP 356 725 A1, EP 700 985 A1 and US 4, 877, 416. In the case of polyethers,
such
products also have carrier oil properties. Typical examples of these are
tridecanol
butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and
polyisobutenol
butoxylates and propoxylates and also the corresponding reaction products with
ammonia.
CA 02549647 2006-06-14
18
Additives containing carboxylic ester groups (vii) are preferably esters of
mono-, di- or
tricarboxylic acids with long-chain alkanols or polyols, in particular those
having a
minimum viscosity of 2 mm2/s at 100°C, as described in particular in DE
38 38 918 A1.
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, from 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.
Additives containing moieties derived from succinic anhydride and having
hydroxyl
and/or amino and/or amido and/or imido groups (viii) are preferably
corresponding
derivatives of polyisobutenylsuccinic anhydride which are obtainable by
reacting
conventional or highly reactive polyisobutene having MN = from 300 to 5000
with malefic
anhydride by a thermal route or via the chlorinated polyisobutene. Particular
interest
attaches to derivatives with aliphatic polyamines such as ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such
gasoline fuel
additives are described in particular in US 4, 849, 572.
Additives containing moieties obtained by Mannich reaction of phenolic
hydroxyl
groups with aldehydes and mono- or polyamines (ix) are preferably reaction
products
of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines
such
as ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine
or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may stem
from
conventional or highly reactive polyisobutene having MN = from 300 to 5000.
Such
"polyisobutene-Mannich bases" are described in particular in EP 831 141 A1.
For a more precise definition of the additives detailed individually,
reference is explicitly
made here to the disclosures of the abovementioned prior art documents.
Dispersants as component c) are, for example, imides, amides, esters and
ammonium
and alkali metal salts of polyisobutenesuccinic anhydrides. These compounds
find use
especially in lubricant oils, but sometimes also as detergents in fuel
compositions.
Further additives and assistants which may, if desired, be present as
component d) of
the inventive packages are
organic solvents, for example alcohols such as methanol, ethanol, propanol,
isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol,
neopentanol or
hexanol, for example glycols such as 1,2-ethylene glycol, 1,2-or 1,3-propylene
glycol,
CA 02549647 2006-06-14
19
1,2-, 2,3- or 1,4-butylene glycol, di- or triethylene glycol or di- or
tripropylene glycol, for
example ethers such as methyl tert-butyl ether, 1,2-ethylene glycol monomethyl
ether
or 1,2-ethylene glycol dimethyl ether, 1,2-ethylene glycol monoethyl ether or
1,2-
ethylene glycol diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol,
tetrahydrofuran or dioxane, for example ketones such as acetone, methyl ethyl
ketone
or diacetone alcohol, for example esters such as methyl acetate, ethyl
acetate, propyl
acetate or butyl acetate, for example lactams such as N-methylpyrrolidinone
(NMP), for
example aliphatic or aromatic hydrocarbons and also mixtures thereof such as
pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene,
ethylbenzene, tetralin, decalin, dimethylnaphthalene or white spirit and, for
example,
mineral oil such as gasoline, kerosene, diesel oil or heating oil,
corrosion inhibitors, for example based on ammonium salts, having a tendency
to form
films, of organic carboxylic acids or of heterocyclic aromatics in the case of
fen-ous
metal corrosion protection,
antioxidants or stabilizers, for example based on amines such as p-
phenylenediamine,
dicyclohexylamine or derivatives thereof or on phenols such as 2,4-di-tert-
butylphenoi
or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid,
demulsifiers,
antistats,
metallocenes such as ferrocene or methylcyclopentadienylmanganese tricarbonyl,
lubricity improvers (lubricity additives) such as certain fatty acids,
alkenylsuccinic
esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil,
amines for reducing the pH of the fuel,
further markers other than anthraquinone derivatives and
dyes.
The concentration of component a), i.e. the at least one anthraquinone
derivative, in
the inventive packages is typically selected in such a magnitude that, after
addition of
the package to the mineral oil, the desired concentration of markers) is
present
therein. Typical concentrations of the markers in the mineral oil are, for
instance, in the
range from 0.01 up to a few 10s of ppm by weight.
CA 02549647 2006-06-14
Component b), i.e. the at least one carrier oil, is present in the inventive
packages
typically in a concentration of from 1 to 50% by weight, in particular from 5
to 30% by
weight, and
5 component c), i.e. the at least one detergent and/or the at least one
dispersant,
typically in a concentration of from 25 to 90% by weight, in particular from
30 to 80% by
weight,
based in each case on the total amount of components a) to c) and, where
present, d),
10 the sum of the individual concentrations of components a) to c) and, where
present d)
adding up to 100% by weight.
When, as component d), corrosion inhibitors, antioxidants or stabilizers,
demulsifiers,
antistats, metallocenes, lubricity improvers and amines to reduce the pH of
the fuel are
15 present in the inventive packages, the sum of their concentrations
typically does not
exceed 10% by weight, based on the total weight of the package (i.e. the total
amount
of components a) to c) and d)), the concentration of the corrosion inhibitors
and
demulsifiers being typically in the range of from in each case about 0.01 to
0.5% by
weight of the total amount of the package.
When, as component d), additional organic solvents (i.e. not already
introduced with
the remaining components) are present in the inventive packages, the sum of
their
concentrations typically does not exceed 20% by weight, based on the total
amount of
the package. These solvents generally stem from solutions of the markers
and/or dyes,
which are added to the packages instead of the pure markers and/or dyes with a
view
to more precise meterability.
When, as component d), further markers other than anthraquinone derivatives
are
present in the inventive packages, their concentration is in turn based on the
content
that they are to have after addition of the packages in mineral oil. That
which was
stated for component a) applies mutatis mutandis.
When, as component d), dyes are present in the inventive packages, their
concentration is typically, for instance, between 0.1 to 5% by weight, based
on the total
amount of the package.
CA 02549647 2006-06-14
21
Examples:
Anthraquinone derivatives shown below were investigated. The compounds 1 to 9
were
synthesized starting from 1,4,5,8-tetrachloroanthraquinone and the
appropriately
substituted anilines by the method described in the document EP 0 323 184 A1.
Compound 1 ~a,,nax- 753 nm, THF)
I
Compound 2 ~a,max- 750 nm, THF)
I
I
Compound 3 ~a.max- 673 nm, THF)
,o ~
~o
CA 02549647 2006-06-14
Compound 4 ~a,max ' 758 nm, THF):
22
H__C._
C~zHzs
C~zHzs
Compound 5 ~a,max = 756 nm, THF)
Compound 6 ~~,max= 756 nm, THF):
CA 02549647 2006-06-14
23
Compound 7 ~~,max- 756 nm, THF):
Compound 8:
Compound 9 ~~,max- 670 nm, THF):
\ NH O HN \
\ \
I / I
\ NH O HN \
I~ I~
The trisubstituted compound was obtained as a by-product in the preparation of
compound 8.
CA 02549647 2006-06-14
r
24
Compound 10 (a,maX 643 nm, THF):
~iz~zs
S.G. 33 (commercially available from BASF Aktiengesellschaft)
Compound 11 (a,,nax- 328 nm, THF)
0
\ \
0
(commercially available from BASF Aktiengesellschaft)
Compound 12 (a,max- 648 nm, THF):
R: mixture of the radicals
O HN~R ~0
\ \
I~ I
O HN~R
S.B. 79 (commercially available from BASF Aktiengesellschaft)
Comparison ~~,max- 770 nm, THF):
The comparative compound used was the phthalocyanine of the following formula:
CH3
N rv
N
H3C
CH3
CA 02549647 2006-06-14
t
(prepared according to Example 1 of WO 98/52950 A1 )
Experiments on storage stability:
5 The test mixture used, of a fuel and lubricant additive concentrate with the
components
contained therein and their particular proportions, is detailed below in Table
1:
Table 1:
Component Chemical composition % by weight
Commercial Polyisobutenamine (PIBA); 70
solution
detergent with PIBA content of 50%
by weight
Commercial Fatty alcohol propoxylate 15
carrier oil
Commercial Dimerized and oligomerized 0.1
fatty
corrosion protectionacids
Commercial Fatty alcohol ethoxylate 0.1
demulsifier
Solvent Xylene 14.8
(Detergent, carrier oil, corrosion protection and demulsifier are commercially
available,
for example, from or via BASF Aktiengesellschaft)
A) The storage stability of compounds 1 to 9 and of the comparative compound
compared to the main constituents, detergent and carrier oil, specified in
Table 1
was investigated. To this end, from 50 to 100 mg of the particular compound
were dissolved in 50 ml of Shellsol AB or, when the solubility of the compound
in
Shellsol AB was insufficient, it was first incipiently dissolved with approx.
5 ml of
isopropanol or NMP and then diluted to 50 ml with Shellsol AB. Subsequently,
the solution was filtered through a fluted paper filter.
From 1 to 3 ml of the filtrate were diluted to 10 ml with detergent or carrier
oil
(corresponding to a concentration of the particular compound of from 0.01 to
0.08%) and measured in 1 mm cuvettes against the corresponding unadditized
reference.
The samples were transferred to 10 ml ampules, sealed in an airtight manner
and
stored in a water bath at 50°C.
CA 02549647 2006-06-14
T
26
The results are reproduced in Tables 2 and 3. All experiments were normalized
to the starting extinction.
Table 2: Comparison of the storage stability at 50°C compared to the
detergent
Compound Storage Wavelength Extinction
time (nm) (normalized)
(h)
Comparison 0 768 1.00
114 0.33
161 0.20
283 0.05
1 425 1.00
2 451 752 0.96
3 475 681 0.98
4 500 758 0.86
5 500 756 1.00
6 500 756 0.98
7 500 756 1.00
9 500 670 1.00
Table 3: Comparison of the storage stability at 50°C compared to the
carrier oil
Compound Storage Wavelength Extinction
time (nm) (normalized)
(h)
4 500 758 0.80
5 500 756 1.00
6 500 756 0.88
7 500 756 0.85
9 500 670 0.90
In the presence of carrier oil, the comparative compound exhibited a
distinctly
sharper decrease in the normalized extinction as a function of time than in
the
case of the presence of detergent. The values were therefore not reproduced.
B) The storage stability of compounds 10 to 12 compared to detergent and the
fuel
and lubricant additive concentrate from Table 1 was investigated. To this end,
solutions having a content of 1 % by weight of compounds 10 to 12 in the
detergent or the fuel and lubricant additive concentrate were prepared and the
normalized extinction was determined as a function of the storage time both at
room temperature and at 40°C. The normalization was to the extinction
value at
CA 02549647 2006-06-14
27
the start of storage (i.e. immediately after preparation of the appropriate
solution).
The results are listed hereinbelow.
Compound 10:
Detergent at room temperature: after storage times of 7 and 14 days, no change
could
be detected in the normalized extinction.
Detergent at 40°C: after storage times of 7 and 14 days, no change
could be detected
in the normalized extinction.
Fuel and lubricant additive concentrate at room temperature: after storage
times of 7
and 14 days, no change could be detected in the normalized extinction.
Fuel and lubricant additive concentrate at 40°C: after storage times of
7 and 14 days,
no change could be detected in the normalized extinction.
Compound 11:
Detergent at room temperature: after storage times of 4, 12, 28 and 42 days,
no
change could be detected in the normalized extinction.
Detergent at 40°C: after storage times of 4, 12, 28 and 42 days, no
change could be
detected in the normalized extinction.
Fuel and lubricant additive concentrate at room temperature: after storage
times of 21
and 28 days, no change in the normalized extinction could be detected.
Fuel and lubricant additive concentrate at 40°C: after storage times of
21 and 28 days,
no change in the normalized extinction could be detected.
CA 02549647 2006-06-14
28
Compound 12:
Detergent at room temperature: after storage times of 4, 12, 28 and 42 days,
substantially no change could be detected in the normalized extinction. The
results are
shown by the following table:
Storage time Extinction
(days) (normalized)
0 1.00
4 1.00
12 0.99
28 0.97
42 0.99
Deter4ent at 40°C: after storage times of 4, 12, 28 and 42 days,
substantially no
change could be detected in the normalized extinction. The results are shown
by the
following table:
Storage time Extinction
(days) (normalized)
0 1.00
4 1.00
12 0.99
28 0.98
42 0.98
