U.S. patent application number 12/482059 was filed with the patent office on 2009-12-17 for use of solubilizers for homogenizing additive concentrates.
This patent application is currently assigned to BASF SE. Invention is credited to Heinrich LUBOJANSKI, Frank-Olaf MAEHLING, Thomas PFEIFFER, Irene TROETSCH-SCHALLER.
Application Number | 20090307964 12/482059 |
Document ID | / |
Family ID | 40942506 |
Filed Date | 2009-12-17 |
United States Patent
Application |
20090307964 |
Kind Code |
A1 |
MAEHLING; Frank-Olaf ; et
al. |
December 17, 2009 |
USE OF SOLUBILIZERS FOR HOMOGENIZING ADDITIVE CONCENTRATES
Abstract
A cold-stabilized fuel oil composition comprising a major
proportion by weight of a middle distillate fuel which boils in the
range of 120-500.degree. C. and minor proportions by weight of (A)
at least one cold flow improver, (B) at least one detergent
additive and (C) at least one cold solubilizer I ##STR00001## which
has at least one radical having at least 4 carbon atoms.
Inventors: |
MAEHLING; Frank-Olaf;
(Mannheim, DE) ; TROETSCH-SCHALLER; Irene;
(Bissersheim, DE) ; LUBOJANSKI; Heinrich;
(Soergenloch, DE) ; PFEIFFER; Thomas;
(Boehl-Iggelheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
40942506 |
Appl. No.: |
12/482059 |
Filed: |
June 10, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61060848 |
Jun 12, 2008 |
|
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|
Current U.S.
Class: |
44/329 |
Current CPC
Class: |
C10L 1/1985 20130101;
C10L 1/19 20130101; C10L 1/08 20130101; C10L 1/143 20130101; C10L
1/224 20130101; C10L 1/1973 20130101; C10L 1/2425 20130101; C10L
1/238 20130101; C10L 1/231 20130101; C10L 10/14 20130101; C10L
1/1966 20130101; C10L 1/1824 20130101; C10L 1/2437 20130101; C10L
10/00 20130101; C10L 1/1963 20130101; C10L 1/198 20130101; C10L
1/1616 20130101; C10L 1/221 20130101; C10L 1/1905 20130101; C10L
1/2475 20130101; C10L 1/1852 20130101; C10L 1/2383 20130101 |
Class at
Publication: |
44/329 |
International
Class: |
C10L 1/232 20060101
C10L001/232 |
Claims
1. The use of at least one solubilizer of the general formula I
##STR00006## in which R.sup.1 denotes a hydrocarbylene radical
having from 1 to 12 carbon atoms or a hydrocarbylene radical which
has from 2 to 12 carbon atoms, is interrupted by one or more
heteroatoms selected from the group of O, S and N, and may in each
case bear one or more functional groups selected from the group of
OH, OR.sup.3, NH.sub.2, NHR.sup.4, NR.sup.4R.sup.5, COOH,
COOR.sup.7, CONHR.sup.4 and CONR.sup.4R.sup.5, where amino groups
may also be present in protonated form and carboxylic acid groups
also in deprotonated form, X is OH, OR.sup.3, NH.sub.2, NHR.sup.4
or NR.sup.4R.sup.5, where, in the case that X together with the
adjacent carbonyl group is a carboxylic acid radical, this radical
is present in deprotonated form and the accompanying cation may be
a hydrocarbyl-substituted ammonium cation selected from the group
of [H.sub.3NR.sup.8].sup.+, [H.sub.2NR.sup.8R.sup.9].sup.+ and
[HNR.sup.8R.sup.9R.sup.10].sup.+, Y is O, S, NH or NR.sup.6, or, in
the case that X is NH.sub.2 or NHR.sup.4, is a chemical bond to X
with formation of an imide structure, where R.sup.2 to R.sup.10 are
each independently hydrocarbyl radicals having from 1 to 30 carbon
atoms, with the proviso that at least one of the R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 radicals has at least 4
carbon atoms, for homogenizing additive concentrates suitable for
additizing fuel oil compositions which consist predominantly of a
middle distillate fuel which boils in the range of 120-500.degree.
C. and/or a renewable fuel, said additive concentrates comprising
(A) at least one cold flow improver, (B) at least one detergent
additive and (C) an inert organic solvent or a mixture of such
solvents.
2. The use of at least one solubilizer I according to claim 1 for
homogenizing additive concentrates which additionally comprise (D)
at least one cetane number improver.
3. The use of at least one solubilizer I according to claim 1 or 2
for homogenizing additive concentrates which comprise (A) from 1 to
50% by weight of at least one cold flow improver, (B) from 0.5 to
40% by weight of at least one detergent additive, (C) from 0 to 80%
by weight of at least one cetane number improver, and (D) from 1 to
60% by weight of an inert organic solvent or of a mixture of such
solvents.
4. The use of at least one solubilizer I according to claims 1 to 3
for homogenizing additive concentrates in an amount of from 1.05 to
15% by weight, based on the total amount of the additive
concentrate.
5. The use of at least one solubilizer I according to claims 1 to 4
for homogenizing additive concentrates comprising, as a cold flow
improver, one or more representatives selected from (Aa) copolymers
of ethylene with at least one further ethylenically unsaturated
monomer; (Ab) comb polymers; (Ac) polyoxyalkylenes; (Ad) polar
nitrogen compounds; (Ae) sulfocarboxylic acids or sulfonic acids or
derivatives thereof; and/or (Af) poly(meth)acrylic esters.
6. The use of at least one solubilizer I according to claim 5 for
homogenizing additive concentrates, comprising, as a cold flow
improver, one or more representatives selected from ethylene-vinyl
acetate copolymers; ethylene-vinyl propionate copolymers;
N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates; the
reaction products of 1 mol of ethylenediaminetetraacetic acid with
4 mol of a dialkylamine; the reaction products of 1 mol of
nitrilotriacetic acid with 3 mol of a dialkylamine; the reaction
products of 1 mol of phthalic anhydride with 2 mol of a
dialkylamine; the reaction products of 1 mol of an
alkenyl-spiro-bislactone with 2 mol of a dialkylamine; C.sub.12- to
C.sub.18-alkyl fumarate-vinyl acetate or C.sub.12- to
C.sub.18-alkyl fumarate-styrene comb polymers; and/or C.sub.14- to
C.sub.20-alkyl itaconate comb polymers.
7. The use of at least one solubilizer I according to claims 1 to 6
for homogenizing additive concentrates, comprising, as detergent
additive (B), one or more amphiphilic substances 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 which is selected from (Ba) mono- or polyamino groups having
up to 6 nitrogen atoms, at least one nitrogen atom having basic
properties; (Bb) nitro groups, if appropriate in combination with
hydroxyl groups; (Bc) hydroxyl groups in combination with mono- or
polyamino groups, at least one nitrogen atom having basic
properties; (Bd) carboxyl groups or their alkali metal or alkaline
earth metal salts; (Be) sulfonic acid groups or their alkali metal
or alkaline earth metal salts; (Bf)
polyoxy-C.sub.2-C.sub.4-alkylene moieties which are terminated by
hydroxyl groups, mono- or polyamino groups, at least one nitrogen
atom having basic properties, or by carbamate groups; (Bg)
carboxylic ester groups; (Bh) moieties which derive from succinic
anhydride and have hydroxyl and/or amino and/or amido and/or imido
groups; and/or (Bi) moieties obtained by Mannich reaction of
substituted phenols with aldehydes and mono- or polyamines.
8. The use of at least one solubilizer I according to claim 7 for
homogenizing additive concentrates, comprising, as detergent
additive (B), one or more derivatives which derive from
polyisobutenylsuccinic anhydride and have amino and/or amido and/or
imido groups.
9. The use of at least one solubilizer I according to claims 1 to 8
for homogenizing additive concentrates in which the inert organic
solvents (C) are selected from hydrocarbons, alcohols, carboxylic
esters or mixtures thereof.
10. The use of at least one solubilizer I according to claims 2 to
9 for homogenizing additive concentrates in which the at least one
cetane number improver (D) is selected from organic nitrates.
11. The use of at least one solubilizer I according to claims 1 to
10 for homogenizing additive concentrates where at least one of the
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 or R.sup.7 radicals in
said solubilizer has at least 10 carbon atoms.
12. The use of at least one solubilizer I according to claims 1 to
10 for homogenizing additive concentrates, where X in said
solubilizer is OH.
13. The use of at least one solubilizer I according to claims 1 to
12 for homogenizing additive concentrates, said solubilizer
deriving from maleic acid or phthalic acid.
14. The use of at least one solubilizer I according to claims 1 to
13 for homogenizing additive concentrates, said solubilizer being a
monoamide of maleic acid or of phthalic acid, in which at least one
of the R.sup.2 or R.sup.6 radicals has at least 10 carbon
atoms.
15. An additive concentrate suitable for additizing fuel oil
compositions which consist predominantly of a middle distillate
fuel which boils in the range of 120-500.degree. C. and/or a
renewable fuel, said additive concentrate comprising at least one
solubilizer of the general formula I ##STR00007## in which R.sup.1
denotes a hydrocarbylene radical having from 1 to 12 carbon atoms
or a hydrocarbylene radical which has from 2 to 12 carbon atoms, is
interrupted by one or more heteroatoms selected from the group of
O, S and N, and may in each case bear one or more functional groups
selected from the group of OH, OR.sup.3, NH.sub.2, NHR.sup.4,
NR.sup.4R.sup.5, COOH, COOR.sup.7, CONHR.sup.4 and
CONR.sup.4R.sup.5, where amino groups may also be present in
protonated form and carboxylic acid groups also in deprotonated
form, X is OH, OR.sup.3, NH.sub.2, NHR.sup.4 or NR.sup.4R.sup.5,
where, in the case that X together with the adjacent carbonyl group
is a carboxylic acid radical, this radical is present in
deprotonated form and the accompanying cation may be a
hydrocarbyl-substituted ammonium cation selected from the group of
[H.sub.3NR.sup.8].sup.+, [H.sub.2NR.sup.8R.sup.9].sup.+ and
[HNR.sup.8R.sup.9R.sup.10].sup.+, Y is O, S, NH or NR.sup.6, or, in
the case that X is NH.sub.2 or NHR.sup.4, is a chemical bond to X
with formation of an imide structure, where R.sup.2 to R.sup.10 are
each independently hydrocarbyl radicals having from 1 to 30 carbon
atoms, with the proviso that at least one of the R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 radicals has at least 4
carbon atoms, in an amount of from 1.05 to 15% by weight, based on
the total amount of the additive concentrate, and (A) at least one
cold flow improver, (B) at least one detergent additive and (C) an
inert organic solvent or a mixture of such solvents.
Description
[0001] The present invention relates to the use of specific
dicarboxylic acid derivatives as solubilizers for homogenizing
additive concentrates which comprise cold flow improvers, detergent
additives, inert organic solvents and if appropriate cetane number
improvers. The invention further relates to additive concentrates
suitable for additizing fuel oil compositions which consist
predominantly of a middle distillate fuel which boils in the range
of 120-500.degree. C. and/or a renewable fuel, said additive
concentrates having the ingredients mentioned.
[0002] In the formulation or storage of additive concentrates
which, as well as cold flow improvers which are typically added to
the diesel fuels and heating oils in the mineral oil refineries,
also comprise detergent additives and cetane number improvers which
form the main constituents of so-called diesel performance
packages, there are frequent occurrences - especially at
temperatures significantly below 20.degree. C.--of flaky
precipitates which cannot be filtered off; attempted filtration can
lead to filter conglutination. At least, such additive concentrates
are, however, generally slightly to highly turbid. The presence of
additionally used organic solvents in the additive concentrates
cannot prevent such flaky precipitates or turbidities. The flaky
precipitates, which usually at first remain more or less dispersed
in the solution, can subsequently lead to severe sedimentation or
to gel formation in the additive concentrate.
[0003] It was therefore an object of the present invention to
stabilize such additive concentrates which comprise both cold flow
improvers and detergent additives, and also inert organic solvents
and if appropriate cetane number improvers, such that the flaky
precipitates or turbidities described do not occur in the course of
formulation and storage of the additive concentrates.
[0004] Accordingly, the use has been found of at least one
solubilizer of the general formula I
##STR00002##
in which [0005] R.sup.1 denotes a hydrocarbylene radical having
from 1 to 12 carbon atoms or a hydrocarbylene radical which has
from 2 to 12 carbon atoms, is interrupted by one or more
heteroatoms selected from the group of O, S and N, and may in each
case bear one or more functional groups selected from the group of
OH, OR.sup.3, NH.sub.2, NHR.sup.4, NR.sup.4R.sup.5, COOH,
COOR.sup.7, CONHR.sup.4 and CONR.sup.4R.sup.5, where amino groups
may also be present in protonated form and carboxylic acid groups
also in deprotonated form, [0006] X is OH, OR.sup.3, NH.sub.2,
NHR.sup.4 or NR.sup.4R.sup.5, where, in the case that X together
with the adjacent carbonyl group is a carboxylic acid radical, this
radical is present in deprotonated form and the accompanying cation
may be a hydrocarbyl-substituted ammonium cation selected from the
group of [H.sub.3NR.sup.8].sup.+, [H.sub.2NR.sup.8R.sup.9].sup.+
and [HNR.sup.8R.sup.9R.sup.10].sup.+, [0007] Y is O, S, NH or
NR.sup.6, or, in the case that X is NH.sub.2 or NHR.sup.4, is a
chemical bond to X with formation of an imide structure, where
R.sup.2 to R.sup.10 are each independently hydrocarbyl radicals
having from 1 to 30 carbon atoms,
[0008] with the proviso that at least one of the R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 radicals has at least 4
carbon atoms,
[0009] for homogenizing additive concentrates suitable for
additizing fuel oil compositions which consist predominantly of a
middle distillate fuel which boils in the range of 120-500.degree.
C. and/or a renewable fuel, said additive concentrates comprising
[0010] (A) at least one cold flow improver, [0011] (B) at least one
detergent additive and [0012] (C) an inert organic solvent or a
mixture of such solvents.
[0013] The additive concentrates mentioned preferably additionally
comprise [0014] (D) at least one cetane number improver.
[0015] However, the action of the solubilizers I used according to
the invention also occurs in principle in additive concentrates
which do not comprise any cetane number improver.
[0016] In a preferred embodiment, the solubilizers I used in
accordance with the invention are used to homogenize additive
concentrates which comprise [0017] (A) from 1 to 50% by weight,
especially from 2 to 40% by weight, in particular from 3 to 20% by
weight, of at least one cold flow improver, [0018] (B) from 0.5 to
40% by weight, preferably from 0.7 to 20% by weight, especially
from 1 to 12% by weight, in particular from 1.5 to 7% by weight, of
at least one detergent additive, [0019] (C) from 1 to 60% by
weight, especially from 3 to 50% by weight, in particular from 5 to
40% by weight, of an inert organic solvent or of a mixture of such
solvents and [0020] (D) from 0 to 80% by weight, especially from 25
to 75% by weight, in particular from 40 to 70% by weight, of at
least one cetane number improver.
[0021] The additive concentrates mentioned may additionally
comprise further ingredients, in which case the sum of all
ingredients adds up to 100% by weight.
[0022] In the context of the present invention, homogenization
shall be understood to mean the prevention or the elimination of
the flaky precipitates or turbidities described above in the
additive concentrates.
[0023] The specific dicarboxylic acid derivatives of the general
formula I used as solubilizers in the present invention are known
from WO 2007/131894. They are recommended there as cold
stabilization enhancers in fuel oil compositions which comprise
customary cold flow improvers and detergent additives, in low
dosages--specifically from 1 to 2000 ppm by weight, based on the
fuel oil composition. Corresponding additive concentrates or
technical problems to be solved with such additive concentrates are
not addressed in WO 2007/131894.
[0024] EP-A 807 676 discloses low-sulfur middle distillate fuels
which, to improve their lubricity, comprise carboxamides, for
example also amides of C.sub.3- to C.sub.40-dicarboxylic acids,
cold flow improvers and ashless dispersants. The additives
mentioned may also be added to the middle distillate fuels in the
form of a concentrate which typically also comprises diluents or
solvents.
[0025] Compounds of the type of the general formula I mentioned are
also known as gasoline fuel additives. For instance, EP-A 301 448
describes alkali metal or alkaline earth metal salts of amides of
di-, tri- or tetracarboxylic acids, for example monoamides of
dicarboxylic acids such as maleic acid, as valve seat wear-reducing
additives for gasoline fuels. Similarly, EP-A 555 006 discloses the
wear-reducing action of dicarboxylic acid derivatives such as the
reaction product of maleic anhydride with a secondary amine to give
the monoamide in the form of the alkali metal salt in internal
combustion engines operated with gasoline fuel.
[0026] EP-A 798 364 describes amides obtained by condensation
reactions of carboxylic acids with aliphatic amines as additives
for diesel fuels for reducing deposits at the injection nozzles,
for increasing the lubricity of the fuel and for reducing the wear
of the injection pumps. These amides are based preferably on
relatively long-chain mono-carboxylic acids, especially having from
8 to 30 carbon atoms, such as oleic acid, and on relatively
long-chain amines, especially those having from 8 to 20 carbon
atoms, such as oleylamine or oleylpropylenediamine. However,
dodecenylsuccinic acid and its anhydride are also mentioned as a
starting material for such amides. The amides mentioned may be used
together with other customary diesel additives such as
low-temperature flow improvers, cetane number improvers,
antioxidants, metal deactivators, rust and corrosion inhibitors,
demulsifiers and foam inhibitors.
[0027] The compounds of the general formula I are dicarboxylic acid
derivatives. Depending on the definition of the variables X and Y,
they are present especially in the form of monoesters,
monothioesters, monoamides, diesters, bisthioesters, diamides or
mixed derivatives having in each case two different functions from
the group of the ester, thioester and amide functions or are joined
to form a cycle via an imide function.
[0028] The variable R.sup.1 in the compounds I is the bridging
member between the two carbonyl carbon atoms. A hydrocarbylene
radical shall be understood here to mean a divalent hydrocarbon
radical of any structure which, however, in accordance with the
definition, may also comprise heteroatoms and/or functional groups.
The hydrocarbenyl radical may be saturated, unsaturated or of
aromatic nature; it may have a linear, branched or cyclic
structure.
[0029] R.sup.1 preferably denotes a linear or branched alkylene
group having from 1 to 12, especially from 2 to 8, in particular
from 2 to 6 carbon atoms, for example methylene, 1,1-ethylene,
1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene,
1,2-hexylene, 1,2-octylene, 1,2-decylene, 1,2-dodecylene,
tetramethylene, pentamethylene or hexamethylene, a 1,2-vinylidene
group of the formula --CH.dbd.CH--, a 1,2-, 1,3- or 1,4-phenylene
group, or a heteroarylene group, for example based on the pyridine
skeleton.
[0030] Compounds of the formula I which comprise benzene or
pyridine skeletons for R.sup.1 are based, for example, on
benzenedi-, -tri- or -tetracarboxylic acids such as phthalic acid
(benzene-1,2-dicarboxylic acid), isophthalic acid
(benzene-1,3-dicarboxylic acid), terephthalic acid
(benzene-1,4-dicarboxylic acid), trimellitic acid
(benzene-1,2,4-tri-carboxylic acid), trimesic acid
(benzene-1,3,5-tricarboxylic acid) or pyromellitic acid
(benzene-1,2,4,5-tetracarboxylic acid) or on pyridinedicarboxylic
acids such as quinolinic acid (pyridine-2,3-dicarboxylic acid),
lutidinic acid (pyridine-2,4-dicarboxylic acid), dipicolinic acid
(pyridine-2,6-dicarboxylic acid) or dinicotinic acid
(pyridine-3,5-dicarboxylic acid). In the case of pyromellitic acid
having 4 carboxyl groups, a doubling of the dicarboxylic acid
structure I can occur, such that the active structure of the
solubilizer of the general formula I occurs twice in the
molecule.
[0031] Hydrocarbylene radicals interrupted by heteroatoms from the
group of O, S and N for R.sup.1 are especially C.sub.1- to
C.sub.12-alkylene groups which comprise, incorporated in their
chain, one, two or three oxygen, sulfur and/or nitrogen atoms,
where, in the case of nitrogen atoms, their free valence is
preferably saturated by a lower alkyl group such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
examples thereof are --CH.sub.2--O--CH.sub.2--,
--CH.sub.2CH.sub.2--O--CH.sub.2--CH.sub.2--,
--CH.sub.2--N(CH.sub.3)--CH.sub.2--,
--CH.sub.2CH.sub.2--N(CH.sub.3)--CH.sub.2--CH.sub.2 and
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--.
[0032] When amino groups are present in protonated form or
carboxylic acid groups in deprotonated form in the compounds of the
general form 1, the accompanying counterions are such that the
compounds I still have sufficient oil solubility. In the case of
protonated amino groups, it is possible, for example, for
carboxylates of long-chain fatty acids or long-chain
alkanesulfonates to occur as anions; for this purpose, preference
is given to using those having at least one C.sub.8- to
C.sub.20-alkyl or -alkenyl radical. In the case of deprotonated
carboxylic acids, preferably hydrocarbyl-substituted ammonium
cations selected from the group of [H.sub.3NR.sup.8].sup.+,
[H.sub.2NR.sup.8R.sup.9].sup.+ and [HNR.sup.8R.sup.9R.sup.10].sup.+
occur as cations; the variables R.sup.8, R.sup.9 and R.sup.10
therein each independently denote preferably linear or branched
alkyl radicals such as methyl, ethyl, vinyl, n-propyl, isopropyl,
1-propenyl, 2-propenyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neooctyl,
nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl,
neoundecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl (stearyl), oleyl, linolyl,
linolenyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl,
tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,
nonacosyl, squalyl or the constitution isomers thereof.
[0033] When the R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 or
R.sup.7 radicals are a hydrocarbyl radical having from 1 to 30
carbon atoms, it shall be understood here to mean a virtually
purely hydrocarbon radical of any structure, which, however,
provided that this does not distort the dominant hydrocarbon
character, may still have, to a small degree, heteroatoms, for
example O or N, and/or functional groups with heteroatoms, for
example OH groups. This hydrocarbyl radical may be of saturated,
unsaturated or aromatic nature; it may have a linear, branched or
cyclic structure.
[0034] In the context of the present invention, such a hydrocarbyl
radical having from 1 to 30 carbon atoms for one of the R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6 or R.sup.7 radicals is
preferably a linear or branched alkyl or alkenyl radical such as
methyl, ethyl, vinyl, n-propyl, isopropyl, 1-propenyl, 2-propenyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl,
heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl,
2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl,
isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl (stearyl), oleyl, linolyl, linolenyl, nonadecyl, eicosyl,
hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, squalyl or their constitutional
isomers. Such relatively long-chain alkyl radicals may also stem
from naturally occurring sources, especially from glycerides or the
parent fatty acids.
[0035] In the context of the present invention, such a hydrocarbyl
radical having from 1 to 30 carbon atoms for one of the R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6 or R.sup.7 radicals may also be
an aryl, alkaryl or arylalkyl radical, for example phenyl,
naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, or
o-, m- or p-xylyl.
[0036] At least one of the R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6 or R.sup.7 radicals in the solubilizers I must have at
least 4, preferably at least 6, especially at least 8, more
preferably at least 10, in particular at least 12 carbon atoms, in
order that the compounds I have the necessary oil solubility. Such
relatively long-chain radicals are typically present in the form of
linear or slightly branched alkyl or alkenyl chains as described
above. The remaining R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 or
R.sup.7 radicals are then typically short-chain, i.e. they have
generally from 1 to 4 carbon atoms, or the corresponding valences
in the compound I are saturated by hydrogen.
[0037] In a preferred embodiment, at least one solubilizer I in
which at least one of the R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6 or R.sup.7 radicals has at least 4, preferably at least 6,
especially at least 8, more preferably at least 10, in particular
at least 12 carbon atoms, is used for the present invention to
homogenize additive concentrates.
[0038] In a further preferred embodiment, at least one solubilizer
I in which the variable X is OH is used for the present invention;
they are then especially dicarboxylic monoesters, dicarboxylic
monothioesters or dicarboxylic monoamides.
[0039] In a further preferred embodiment, at least one solubilizer
I which derives from maleic acid or phthalic acid, i.e. the
bridging member R.sup.1 is a 1,2-vinylidene group of the formula
--CH.dbd.CH-- or a 1,2-phenylene group, is used for the present
invention.
[0040] More preferably, the solubilizer I used in accordance with
the invention is a monoamide of maleic acid or of phthalic acid
(Y.dbd.NR.sup.6), in which at least one of the R.sup.2 and R.sup.6
radicals has at least 10 and especially at least 12 carbon atoms.
Such maleic and phthalic monoamides satisfy the formula
HOOC--R.sup.1--CO--NR.sup.2R.sup.6 (R.sup.1=1,2-vinylidene or
1,2-phenylene) in which one of the R.sup.2 and R.sup.6 radicals or
both R.sup.2 and R.sup.6 radicals are a hydrocarbyl radical having
from 10 to 30 and from 12 to 30 carbon atoms respectively. One
example thereof is the monoamide of maleic acid or phthalic acid
and tridecylamine (R.sup.2=tridecyl, R.sup.6=H), which is
obtainable in a known manner by reacting maleic acid or maleic
anhydride, or phthalic acid or phthalic anhydride, with
tridecylamine in an equimolar ratio. Preference is given here to
using a tridecylamine which is present in the form of a mixture of
structural isomers of n-tridecylamine and branched tridecylamines,
where the proportion of n-tridecylamine is generally less than 70
mol%, especially less than 50 mol %, in particular less than 35 mol
%.
[0041] The solubilizers I used in accordance with the invention are
present in the additive concentrates generally in an amount of from
1.05 to 15% by weight, preferably from 1.25 to 13.5% by weight,
more preferably from 1.5 to 12% by weight, especially from 2.0 to
10% by weight, in particular from 2.5 to 7% by weight, based in
each case on the total amount of the additive concentrate. In most
cases, the preferred ranges mention-ed are sufficient to obtain a
sufficient homogenizing action in the additive concentrates.
However, it is also possible to use more than 15% by weight of
solubilizers 1, for example up to 20 or up to 30% by weight, but no
further significant enhancement of the desired effect is thus
achieved. In contrast to the upper limit, the lower limit for the
amount of solubilizers I used in accordance with the invention is
critical; it has been found that amounts up to 1% by weight are
frequently still not sufficient to obtain the desired
homogenization.
[0042] In the context of the present invention, cold flow improvers
of component (A) shall be understood to mean all additives which
improve the cold properties of fuel oil compositions. In addition
to the actual cold flow improvers ("MDFIs", for example
ethylenevinyl acetate copolymers), these are in particular also
nucleators, paraffin dispersants ("WASAs", for example certain
polar nitrogen compounds) or the combination of MDFIs and WASAs
("WAFIs") (cf. also Ullmann's Encyclopedia of Industrial Chemistry,
5th edition, Volume A16, p. 719 ff.).
[0043] Such cold flow improvers for the present invention as
component [0044] (A) should advantageously be one or more
representatives selected from [0045] (Aa) copolymers of ethylene
with at least one further ethylenically unsaturated monomer; [0046]
(Ab) comb polymers; [0047] (Ac) polyoxyalkylenes; [0048] (Ad) polar
nitrogen compounds; [0049] (Ae) sulfocarboxylic acids or sulfonic
acids or derivatives thereof; and/or (Af) poly(meth)acrylic
esters.
[0050] In the copolymers of ethylene with at least one further
ethylenically unsaturated monomer of group (Aa), the monomer is
preferably selected from alkenylcarboxylic esters, (meth)acrylic
esters and olefins.
[0051] Suitable olefins are, for example, those having from 3 to 10
carbon atoms and having from 1 to 3, preferably having 1 or 2
carbon-carbon double bonds, in particular having one carbon-carbon
double bond. In the latter case, the carbon-carbon double bond may
be arranged either terminally (.alpha.-olefins) or internally.
However, preference is given to .alpha.-olefins, particular
preference to .alpha.-olefins having from 3 to 8 carbon atoms, such
as propene, 1-butene, 1-pentene, 1-hexene and 1-octene.
[0052] Suitable (meth)acrylic esters are, for example, esters of
(meth)acrylic acid with C.sub.1-C.sub.14-alkanols, especially with
methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol,
isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol,
2-ethylhexanol, nonanol, decanol, 2-propylheptanol, dodecanol and
tetradecanol.
[0053] Suitable alkenylcarboxylic esters are, for example, the
vinyl and propenyl esters of carboxylic acids having from 2 to 20
carbon atoms whose hydrocarbon radical may be linear or branched.
Among these, preference is given to the vinyl esters. Among the
carboxylic acids having a branched hydrocarbon radical, preference
is given to those whose branch is disposed in the .alpha.-position
to the carboxyl group, and particular preference is given to the
.alpha.-carbon atom being tertiary, i.e. the carboxylic acid is a
neocarboxylic acid. However, preference is given to the hydrocarbon
radical of the carboxylic acid being linear.
[0054] Examples of suitable alkenylcarboxylic esters are vinyl
acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate,
vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl
neodecanoate and the corresponding propenyl esters, preference
being given to the vinyl esters. A particularly preferred
alkenylcarboxylic ester is vinyl acetate; typical copolymers of
group (Aa) resulting therefrom are ethylene-vinyl acetate
copolymers ("EVA"), which are used in diesel fuels on a large
scale.
[0055] Particular preference is given to the ethylenically
unsaturated monomer being selected from alkenylcarboxylic
esters.
[0056] Also suitable are copolymers which comprise two or more
different copolymerized alkenylcarboxylic esters which differ in
the alkenyl function and/or in the carboxylic acid group. Likewise
suitable are copolymers which, in addition to the alkenylcarboxylic
ester(s), comprise at least one copolymerized olefin and/or at
least one copolymerized (meth)acrylic ester.
[0057] The ethylenically unsaturated monomer is copolymerized in
the copolymer of group (Aa) in an amount of preferably from 1 to 50
mol %, more preferably from 10 to 50 mol % and in particular from 5
to 20 mol %, based on the overall copolymer.
[0058] The copolymer of group (Aa) preferably has a number-average
molecular weight Mn of from 500 to 20 000, more preferably from
7500 to 10 000 and in particular from 1000 to 6000.
[0059] Comb polymers of group (Ab) are, for example, those
described in "Comb-Like Polymers. Structure and Properties", N. A.
Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8,
pages 117 to 253 (1974). Among those described there, suitable comb
polymers are, for example, those of the formula II
##STR00003##
where [0060] D is R.sup.17, COOR.sup.17, OCOR.sup.17, R.sup.18,
OCOR.sup.17 or OR.sup.17, [0061] E is H, CH.sub.3, D or R.sup.18,
[0062] G is H or D, [0063] J is H, R.sup.18, R.sup.18COOR.sup.17,
aryl or heterocyclyl, [0064] K is H, COOR.sup.18, OCOR.sup.18,
OR.sup.18 or COOH, [0065] L is H, R.sup.18, COOR.sup.18,
OCOR.sup.18, COOH or aryl, where [0066] R.sup.17 is a hydrocarbon
radical having at least 10 carbon atoms, preferably having from 10
to 30 carbon atoms, [0067] R.sup.18 is a hydrocarbon radical having
at least one carbon atom, preferably having from 1 to 30 carbon
atoms, [0068] m is a molar fraction in the range from 1.0 to 0.4
and [0069] n is a molar fraction in the range from 0 to 0.6.
[0070] Preferred comb polymers are, for example, obtainable by
copolymerization of maleic anhydride or fumaric acid with another
ethylenically unsaturated monomer, for example with an
.alpha.-olefin or an unsaturated ester, such as vinyl acetate, and
subsequent esterification of the anhydride or acid function with an
alcohol having at least 10 carbon atoms. Further preferred comb
polymers are copolymers of .alpha.-olefins and esterified
comonomers, for example esterified copolymers of styrene and maleic
anhydride or esterified copolymers of styrene and fumaric acid.
Also suitable are mixtures of comb polymers. Comb polymers may also
be polyfumarates or polymaleates. Homo- and copolymers of vinyl
ethers are also suitable comb polymers.
[0071] Suitable polyoxyalkylenes of group (Ac) are, for example,
polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof.
The polyoxyalkylene compounds preferably comprise at least one
linear alkyl group, more preferably at least two linear alkyl
groups, having from 10 to 30 carbon atoms and a polyoxyalkylene
group having a molecular weight of up to 5000. The alkyl group of
the polyoxyalkylene radical preferably comprises from 1 to 4 carbon
atoms. Such polyoxyalkylene compounds are described, for example,
in EP-A-0 061 895 and also in U.S. Pat. No. 4,491,455, which are
hereby fully incorporated by reference. Preferred polyoxyalkylene
esters, ethers and ester/ethers have the general formula Ill
R.sup.19[O--(CH.sub.2).sub.y].sub.xO--R.sup.20 (III)
in which [0072] R.sup.19 and R.sup.20 are each independently
R.sup.21, R.sup.21--CO--, R.sup.21--O--CO(CH.sub.2).sub.2-- or
R.sup.21--O--CO(CH.sub.2).sub.2-- [0073] CO-- where R.sup.21 is
linear C.sub.1-C.sub.30-alkyl, [0074] y is from 1 to 4, [0075] x is
from 2 to 200, and [0076] z is from 1 to 4.
[0077] Preferred polyoxyalkylene compounds of the formula III in
which both R.sup.19 and R.sup.20 are R.sup.21 are polyethylene
glycols and polypropylene glycols having a number-average molecular
weight of from 100 to 5000. Preferred polyoxyalkylenes of the
formula III in which one of the R.sup.19 radicals is R.sup.21 and
the other is R.sup.21--CO-- are polyoxyalkylene esters of fatty
acids having from 10 to 30 carbon atoms, such as stearic acid or
behenic acid. Preferred polyoxyalkylene compounds in which both
R.sup.19 and R.sup.20 are an R.sup.21--CO-- radical are diesters of
fatty acids having from 10 to 30 carbon atoms, preferably of
stearic acid or behenic acid.
[0078] The polar nitrogen compounds of group (Ad), which are
advantageously oil-soluble, may be either ionic or nonionic and
preferably have at least one substituent, more preferably at least
2 substituents, of the formula >NR.sup.22 in which R.sup.22 is a
C.sub.8-C.sub.40-hydrocarbon radical. The nitrogen substituents may
also be quaternized, i.e. be in cationic form. An example of such
nitrogen compounds is that of ammonium salts and/or amides which
are obtainable by the reaction of at least one amine substituted by
at least one hydrocarbon radical with a carboxylic acid having from
1 to 4 carboxyl groups or with a suitable derivative thereof. The
amines preferably comprise at least one linear
C.sub.8-C.sub.40-alkyl radical. Suitable primary amines are, for
example, octylamine, nonylamine, decylamine, undecylamine,
dodecylamine, tetradecylamine and the higher linear homologs.
Suitable secondary amines are, for example, dioctadecylamine and
methylbehenylamine. Also suitable are amine mixtures, in particular
amine mixtures obtainable on the industrial scale, such as fatty
amines or hydrogenated tallamines, as described, for example, in
Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition,
"Amines, aliphatic" chapter. Acids suitable for the reaction are,
for example, cyclo-hexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-di-carboxylic
acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic
acid, terephthalic acid and succinic acids substituted with
long-chain hydrocarbon radicals.
[0079] A further example of polar nitrogen compounds of group (Ad)
is that of ring systems which bear at least two substituents of the
formula -A-NR.sup.23R.sup.24 in which A is a linear or branched
aliphatic hydrocarbon group which is optionally interrupted by one
or more groups selected from O, S, NR.sup.35 and CO, and R.sup.23
and R.sup.24 are each a C.sub.9-C.sub.40-hydrocarbon radical which
is optionally interrupted by one or more groups selected from O, S,
NR.sup.35 and CO, and/or substituted by one or more substituents
selected from OH, SH and NR.sup.35R.sup.36 where R.sup.35 is
C.sub.1-C.sub.40-alkyl which is optionally interrupted by one or
more moieties selected from CO, NR.sup.35, O and S, and/or
substituted by one or more radicals selected from
NR.sup.37R.sup.38, OR.sup.37, SR.sup.37, COR.sup.37, COOR.sup.37,
CONR.sup.37R.sup.38, aryl or heterocyclyl, where R.sup.37 and
R.sup.38 are each independently selected from H or
C.sub.1-C.sub.4-alkyl; and R.sup.36 is H or R.sup.35.
[0080] A is preferably a methylene or polymethylene group having
from 2 to 20 methylene units. Examples of suitable R.sup.23 and
R.sup.24 radicals are 2-hydroxyethyl, 3-hydroxypropyl,
4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The
cyclic system may be homocyclic, heterocyclic, fused polycyclic or
nonfused polycyclic systems. The ring system is preferably carbo-
or heteroaromatic, in particular carboaromatic. Examples of such
polycyclic ring systems are fused benzoid structures such as
naphthalene, anthraxcene, phenanthrene and pyrene, fused nonbenzoid
structures such as azulene, indene, hydrindene and fluorene,
nonfused polycycles such as diphenyl, heterocycles such as
quinoline, indole, dihydroindole, benzofuran, coumarin,
isocoumarin, benzothiophene, carbazole, diphenylene oxide and
diphenylene sulfide, nonaromatic or partially saturated ring
systems such as decalin, and three-dimensional structures such as
.alpha.-pinene, camphene, bornylene, norbornane, norbornene,
bicyclooctane and bicyclooctene.
[0081] A further example of suitable polar nitrogen compounds is
that of condensates of long-chain primary or secondary amines with
carboxyl group-containing polymers.
[0082] The polar nitrogen compounds mentioned here are described in
WO 00/44857 and also in the references cited therein, which are
hereby fully incorporated by reference.
[0083] Suitable polar nitrogen compounds are also described, for
example, in DE-A-198 48 621, DE-A-196 22 052 or EP-B 398 101, which
are hereby incorporated by reference.
[0084] Suitable sulfo carboxylic acids/sulfonic acids or their
derivatives of group (Ae) are, for example, those of the general
formula IV
##STR00004##
in which [0085] Y' is
SO.sub.3.sup.-(NR.sup.25.sub.3R.sup.26).sup.+,
SO.sub.3.sup.-(NHR.sup.25.sub.2R.sup.26).sup.+,
SO.sub.3.sup.-(NH.sub.2R.sup.25R.sup.26),
SO.sub.3.sup.-(NH.sub.3R.sup.26) or [0086]
SO.sub.2NR.sup.25R.sup.26, [0087] X' is Y', CONR.sup.25R.sup.27,
CO.sub.2.sup.-(NR.sup.25.sub.3R.sup.27).sup.+,
CO.sub.2.sup.-(NHR.sup.25.sub.2R.sup.27).sup.+,
R.sup.28--COOR.sup.27, NR.sup.25COR.sup.27, R.sup.28OR.sup.27,
R.sup.28OCOR.sup.27, R.sup.28R.sup.27, N(COR.sup.25)R.sup.27 or
Z-(NR.sup.25.sub.3R.sup.27).sup.+, [0088] where [0089] R.sup.25 is
a hydrocarbon radical, [0090] R.sup.26 and R.sup.27 are each alkyl,
alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in
the main chain, [0091] R.sup.28 is C.sub.2-C.sub.5-alkylene, [0092]
Z-- is one anion equivalent and [0093] A' and B are each alkyl,
alkenyl or two substituted hydrocarbon radicals or, together with
the carbon atoms to which they are bonded, form an aromatic or
cycloaliphatic ring system.
[0094] Such sulfo carboxylic acids and sulfonic acids and their
derivatives are described in EP-A-0 261 957, which is hereby fully
incorporated by reference.
[0095] Suitable poly(meth)acrylic esters of group (Af) are either
homo- or copolymers of acrylic and methacrylic esters. Preference
is given to copolymers of at least two different (meth)acrylic
esters which differ in the esterified alcohol. Optionally, the
copolymer comprises another different copolymerized olefinically
unsaturated monomer. The weight-average molecular weight of the
polymer is preferably from 50 000 to 500 000. A particularly
preferred polymer is a copolymer of methacrylic acid and
methacrylic esters of saturated C.sub.14- and C.sub.15-alcohols, in
which the acid groups have been neutralized with hydrogenated
tallamine. Suitable poly(meth)acrylic esters are described, for
example, in WO 00/44857, which is hereby fully incorporated by
reference.
[0096] The additive concentrates mentioned preferably comprise, as
component (A), at least one cold flow improver of group (Aa) or a
mixture of one or more cold flow improvers of group (Aa) and one or
more cold flow improvers selected from the remaining groups (Ab) to
(Af), especially a mixture of one or more cold flow improvers of
group (Aa) and one or more cold flow improvers of group (Ad).
[0097] More preferably, the additive concentrates mentioned
comprise, as cold flow improvers of components (A), one or more
representatives selected from [0098] ethylene-vinyl acetate
copolymers [representatives of group (Aa)]; [0099] ethylene-vinyl
propionate copolymers [representatives of group (Aa)]; [0100]
N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates
[representatives of group (Ad)], for example the reaction product
formed from 1 mol of phthalic anhydride and 2 mol of ditallow fatty
amine, the latter being hydrogenated or unhydrogenated; [0101] the
reaction products of 1 mol of ethylenediaminetetraacetic acid with
4 mol of a dialkylamine [representatives of group (Ad)], for
example the reaction product formed from 1 mol of
ethylenediaminetetraacetic acid and 4 mol of ditallow fatty amine,
the latter being hydrogenated or unhydrogenated; [0102] the
reaction products of 1 mol of nitrilotriacetic acid with 3 mol of a
dialkylamine [representatives of group (Ad)], for example the
reaction product formed from 1 mol of nitrilotriacetic acid and 3
mol of ditallow fatty amine, the latter being hydrogenated or
unhydrogenated; [0103] the reaction products of 1 mol of phthalic
anhydride with 2 mol of a dialkylamine [representatives of group
(Ad)], for example the reaction product formed from 1 mol of
phthalic anhydride and 2 mol of ditallow fatty amine, the latter
being hydrogenated or unhydrogenated; [0104] the reaction products
of 1 mol of an alkenyl-spiro-bislactone with 2 mol of a
dialkylamine [representatives of group (Ad)], for example the
reaction product formed from 1 mol of an alkenyl-spiro-bislactone
with 2 mol of ditallow fatty amine and/or tallow fatty amine, the
latter two being hydrogenated or unhydrogenated; [0105] C.sub.12-
to C.sub.18-alkyl fumarate-vinyl acetate or C.sub.12- to
C.sub.18-alkyl fumarate-styrene comb polymers [representatives of
group (Ab)], for example those in the molar ratio of the two
monomer types of 1:1; and/or [0106] C.sub.14- to C.sub.20-alkyl
itaconate comb polymers [representatives of group (Ab)].
[0107] The detergent additives of component (B) to be used in the
additive concentrates mentioned are generally advantageously
amphiphilic substances 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 which is
selected from [0108] (Ba) mono- or polyamino groups having up to 6
nitrogen atoms, at least one nitrogen atom having basic properties;
[0109] (Bb) nitro groups, if appropriate in combination with
hydroxyl groups; [0110] (Bc) hydroxyl groups in combination with
mono- or polyamino groups, at least one nitrogen atom having basic
properties; [0111] (Bd) carboxyl groups or their alkali metal or
alkaline earth metal salts; [0112] (Be) sulfonic acid groups or
their alkali metal or alkaline earth metal salts; [0113] (Bf)
polyoxy-C.sub.2-C.sub.4-alkylene moieties which are terminated by
hydroxyl groups, mono- or polyamino groups, at least one nitrogen
atom having basic properties, or by carbamate groups; [0114] (Bg)
carboxylic ester groups; [0115] (Bh) moieties which derive from
succinic anhydride and have hydroxyl and/or amino and/or amido
and/or imido groups; and/or [0116] (Bi) moieties obtained by
Mannich reaction of substituted phenols with aldehydes and mono- or
polyamines.
[0117] The hydrophobic hydrocarbon radical in the above detergent
additives, which ensures the adequate solubility in the fuel oil
composition, has a number-average molecular weight (Mn) of from 85
to 20 000, especially from 113 to 10 000, in particular from 300 to
5000. Typical hydrophobic hydrocarbon radicals, especially in
conjunction with the polar moieties (Ba), (Bc), (Bh) and (Bi),
include relatively long-chain alkyl or alkenyl groups, especially
the polypropenyl, polybutenyl and polyisobutenyl radical, each
having Mn=from 300 to 5000, especially from 500 to 2500, in
particular from 700 to 2300.
[0118] Examples of the above groups of detergent additives include
the following:
[0119] Additives comprising mono- or polyamino groups (Ba) are
preferably polyalkenemono- or polyalkenepolyamines based on
polypropene or conventional (i.e. having predominantly internal
double bonds) polybutene or polyisobutene having Mn=from 300 to
5000. When polybutene or polyisobutene having predominantly
internal double bonds (usually in the beta- and gamma-position) 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, for example, ammonia, monoamines or
polyamines, such as dimethylaminopropylamine, ethylenediamine,
diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Corresponding additives based on polypropene are described in
particular in WO-A-94/24231.
[0120] Further preferred additives comprising monoamino groups (Ba)
are the hydrogenation products of the reaction products of
polyisobutenes having an average degree of polymerization P of from
5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and
oxygen, as described in particular in WO-A-97/03946.
[0121] Further preferred additives comprising monoamino groups (Ba)
are the compounds obtainable from polyisobutene epoxides by
reaction with amines and subsequent dehydration and reduction of
the amino alcohols, as described in particular in DE-A-196 20
262.
[0122] Additives comprising nitro groups (Bb), if appropriate in
combination with hydroxyl groups, are preferably reaction products
of polyisobutenes having an average degree of polymerization P=from
5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of
nitrogen oxides and oxygen, as described in particular in
WO-A-96/03367 and WO-A-96/03479. These reaction products are
generally mixtures of pure nitropoly-isobutenes (e.g.
.alpha.,.beta.-dinitropolyisobutene) and mixed
hydroxynitropolyiso-butenes (e.g.
.alpha.-nitro-.beta.-hydroxypolyisobutene).
[0123] Additives comprising hydroxyl groups in combination with
mono- or polyamino groups (Bc) 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-A 476 485.
[0124] Additives comprising carboxyl groups or their alkali metal
or alkaline earth metal salts (Bd) are preferably copolymers of
C.sub.2-C.sub.40-olefins with maleic 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-A-307 815. Such additives serve mainly to prevent
valve seat wear and can, as described in WO-A-87/01126,
advantageously be used in combination with customary fuel
detergents such as poly(iso)buteneamines or polyetheramines.
[0125] Additives comprising sulfonic acid groups or their alkali
metal or alkaline earth metal salts (Be) are preferably alkali
metal or alkaline earth metal salts of an alkyl sulfosuccinate, as
described in particular in EP-A-639 632. Such additives serve
mainly to prevent valve seat wear and can be used advantageously in
combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
[0126] Additives comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties (Bf) are preferably polyethers or polyether amines which
are obtainable by reaction of C.sub.2-C.sub.60-alkanols,
C.sub.6-C.sub.30-alkane-diols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with 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 polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. In the
case of polyethers, such products also have carrier oil properties.
Typical examples of these are tridecanol butoxylates, isotridecanol
butoxylates, isononylphenol butoxylates and polyisobutenol
butoxylates and propoxylates and also the corresponding reaction
products with ammonia.
[0127] Additives comprising carboxylic ester groups (Bg) are
preferably esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, in particular those having a
minimum viscosity of 2 mm.sup.2/s at 100.degree. C., as described
in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic
acids used may be aliphatic or aromatic acids, and particularly
suitable ester alcohols or ester polyols are long-chain
representatives having, for example, 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.
[0128] Additives comprising moieties derived from succinic
anhydride and having hydroxyl and/or amino and/or amido and/or
imido groups (Bh) are preferably corresponding derivatives of
alkyl- or alkenyl-substituted succinic anhydride and especially the
corresponding derivatives of polyisobutenylsuccinic anhydride which
are obtainable by reacting conventional or highly reactive
polyisobutene having Mn=from 300 to 5000 with maleic 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. The moieties having hydroxyl and/or amino
and/or amido and/or imido groups are, for example, carboxylic acid
groups, acid amides of monoamines, acid amides of di- or polyamines
which, in addition to the amide function, also have free amine
groups, succinic acid derivatives having an acid and an amide
function, carboximides with monoamines, carboximides with di- or
polyamines which, in addition to the imide function, also have free
amine groups, or diimides which are formed by the reaction of di-
or polyamines with two succinic acid derivatives. Such fuel
additives are described in particular in U.S. Pat. No.
4,849,572.
[0129] Additives comprising moieties (Bi) obtained by Mannich
reaction of substituted phenols with aldehydes and mono- or
polyamines are preferably reaction products of
polyisobutene-substituted phenols with formaldehyde and mono- or
polyamines such as ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dimethylaminopropylamine. The polyisobutenyl-substituted phenols
may stem from conventional or highly reactive polyisobutene having
Mn=from 300 to 5000. Such "polyisobutene-Mannich bases" are
described in particular in EP-A-831 141.
[0130] For a more precise definition of the fuel additives detailed
individually, reference is explicitly made here to the disclosures
of the abovementioned prior art documents. Particular preference is
given to detergent additives from group (Bh). These are preferably
the reaction products of alkyl- or alkenyl-substituted succinic
anhydrides, especially of polyisobutenylsuccinic anhydrides, with
amines. It will be appreciated that these reaction products are not
obtainable only when substituted succinic anhydride is used, but
also when substituted succinic acid or suitable acid derivatives,
such as succinyl halides or succinic esters, are used.
[0131] In a particularly preferred embodiment, the additive
concentrates mentioned comprise, as a detergent additive of
component (B), one or more derivatives which have been derived from
polyisobutenylsuccinic anhydride and have amino and/or amido and/or
imido groups. Particularly preferred detergent additives in this
context are polyisobutenyl-substituted succinimides, especially the
imides with aliphatic polyamines. Particularly preferred polyamines
are diethylenetriamine, tetraethylenepentamine and
pentaethylenehexamine, particular preference being given to
tetraethylenepentamine. The polyisobutenyl radical has a
number-average molecular weight Mn of preferably from 500 to 5000,
more preferably from 500 to 2000 and in particular of about
1000.
[0132] In a further preferred embodiment, the detergent additives
mentioned are used in combination with at least one carrier oil in
the additive concentrates mentioned. Suitable mineral carrier oils
are the fractions obtained in crude oil processing, such as
brightstock or base oils having viscosities, for example, from the
SN 500-2000 class; but also aromatic hydrocarbons, paraffinic
hydrocarbons and alkoxyalkanols. Likewise useful is a fraction
which is obtained in the refining of mineral oil and is known as
"hydrocrack oil" (vacuum distillate cut having a boiling range of
from about 360 to 500.degree. C., obtainable from natural mineral
oil which has been catalytically hydrogenated under high pressure
and isomerized and also deparaffinized). Likewise suitable are
mixtures of abovementioned mineral carrier oils.
[0133] Examples of suitable synthetic carrier oils are selected
from: polyolefins (poly-alpha-olefins or poly(internal olefin)s),
(poly)esters, (poly)alkoxylates, polyethers, aliphatic polyether
amines, alkylphenol-started polyethers, alkylphenol-started
polyether amines and carboxylic esters of long-chain alkanols.
[0134] Examples of suitable polyolefins are olefin polymers having
Mn=from 400 to 1800, in particular based on polybutene or
polyisobutene (hydrogenated or unhydrogenated).
[0135] Examples of suitable polyethers or polyetheramines are
preferably compounds comprising polyoxy-C.sub.2-C.sub.4-alkylene
moieties which are obtainable by reacting
C.sub.2-C.sub.60-alkanols, C.sub.6-C.sub.30-alkanediols, mono- or
di-C.sub.2-C.sub.30-alkylamines,
C.sub.1-C.sub.30-alkylcyclohexanols or
C.sub.1-C.sub.30-alkylphenols with from 1 to 30 mol of ethylene
oxide and/or propylene oxide and/or butylene oxide per hydroxyl
group or amino group, and, in the case of the polyether amines, by
subsequent reductive amination with ammonia, monoamines or
polyamines. Such products are described in particular in EP-A-310
875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416. For
example, the polyether amines used may be
poly-C.sub.2-C.sub.6-alkylene oxide amines or functional
derivatives thereof. Typical examples thereof are tridecanol
butoxylates or isotridecanol butoxylates, isononylphenol
butoxylates and also polyisobutenol butoxylates and propoxylates,
and also the corresponding reaction products with ammonia.
[0136] Examples of carboxylic esters of long-chain alkanols are in
particular esters of mono-, di- or tricarboxylic acids with
long-chain alkanols or polyols, as described in particular in
DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be
aliphatic or aromatic acids; suitable ester alcohols or polyols are
in particular long-chain representatives having, for example, from
6 to 24 carbon atoms. Typical representatives of the esters are
adipates, phthalates, isophthalates, terephthalates and
trimellitates of isooctanol, isononanol, isodecanol and
isotridecanol, for example di-(n- or isotridecyl) phthalate.
[0137] Further suitable carrier oil systems are described, for
example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0
452 328 and EP-A-0 548 617, which are explicitly incorporated
herein by way of reference.
[0138] Examples of particularly suitable synthetic carrier oils are
alcohol-started polyethers having from about 5 to 35, for example
from about 5 to 30, C.sub.3-C.sub.6-alkylene oxide units, for
example selected from propylene oxide, n-butylene oxide and
isobutylene oxide units, or mixtures thereof. Nonlimiting examples
of suitable starter alcohols are long-chain alkanols or phenols
substituted by long-chain alkyl in which the long-chain alkyl
radical is in particular a straight-chain or branched
C.sub.6-C.sub.18-alkyl radical. Preferred examples include
tridecanol and nonylphenol.
[0139] Further suitable synthetic carrier oils are alkoxylated
alkylphenols, as described in DE-A-10 102 913.6.
[0140] Preferred carrier oils are synthetic carrier oils,
particular preference being given to polyethers.
[0141] When a carrier oil is also incorporated into the additive
concentrate, it is added typically in an amount of from 10% by
weight to 100% by weight, preferably from 20 to 70% by weight,
based in each case on the amount of detergent additive of component
(B).
[0142] The inert organic solvents or solvent mixtures of component
(C) used in the additive concentrates mentioned are generally those
which are selected from hydrocarbons, alcohols, carboxylic esters
or mixtures thereof. "Inert" means here that such organic solvents
exert no significant interactions, if any, with the active
components in the additive concentrates or enter into chemical
reactions with them under use conditions. Such inert organic
solvents or solvent mixtures are essentially free of further
organic compounds with functional groups. Typical hydrocarbon
solvents suitable as component (C) are n-pentane, n-hexane,
n-heptane, cyclohexane, methylcyclohexane, toluene, xylenes,
technical hydrocarbon mixtures such as Solvent Naphtha, as are
commercially obtainable, for example, under the name Solvesso.RTM.
150, and fuels themselves. Typical alcohols suitable as component
(C) are methanol, ethanol, n-propanol, isopropanol, n-butanol,
tert-butanol, 2-ethylhexanol and 2-propylheptanol. Carboxylic
esters suitable as component (C) are, for example, fatty acid lower
alkyl esters, especially fatty acid methyl esters.
[0143] The cetane number improvers of component (D) are also
referred to as ignition or combustion improvers. The component (D)
to be used in the additive concentrates mentioned is preferably at
least one cetane number improver which is selected from organic
nitrates. Such organic nitrates are especially nitrate esters of
unsubstituted or substituted, aliphatic or cycloaliphatic alcohols,
usually having up to about 10 and in particular having from 2 to 10
carbon atoms. The alkyl group in these nitrate esters may be linear
or branched, saturated or unsaturated. Typical examples of such
nitrate esters are methyl nitrate, ethyl nitrate, n-propyl nitrate,
isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl
nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate,
isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate,
n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl
nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate,
n-decyl nitrate, 2-propylheptyl nitrate, cyclopentyl nitrate,
cyclohexyl nitrate, methylcyclohexyl nitrate and
isopropylcyclohexyl nitrate. Additionally suitable are, for
example, nitrate esters of alkoxy-substituted aliphatic alcohols,
such as 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate,
1-methoxypropyl nitrate or 4-ethoxybutyl nitrate. Also suitable are
diol nitrates such as 1,6-hexamethylene dinitrate. Among the cetane
number improver classes mentioned, primary amyl nitrates, primary
hexyl nitrates, octyl nitrates and mixtures thereof are
preferred.
[0144] Particular preference is given to 2-ethylhexyl nitrate as
component (D). 2-Ethylhexyl nitrate may be present as the sole
cetane number improver or in a mixture with other cetane number
improvers.
[0145] In addition, the additive concentrates mentioned may
comprise further customary coadditives, especially boosters for the
cold flow improvers (A), such as oleic acid-diethylenetriamine
reaction products, corrosion inhibitors, deicing agents such as
ethylene glycol mono- or dimethyl ethers, demulsifiers, dehazers,
antifoams, lubricity improvers, metal deactivators, antioxidants or
stabilizers, antistats, metallocenes, markers and/or dyes. These
customary coadditives are, if desired, added in amount relative to
the components (A) to (C) or (A) to (D) which are customary
therefor.
[0146] In the context of the present invention, fuel oil
compositions shall be understood to mean middle distillate fuels
which boil within the range of 120-500.degree. C., renewable fuels
and mixtures thereof. Such middle distillate fuels are in
particular diesel fuel, heating oil or kerosene, particular
preference being given to heating oil and in particular diesel
fuel. Such renewable fuels are bioethanol and in particular
biodiesel.
[0147] The heating oils are, for example, low-sulfur or sulfur-rich
crude oil raffinates or bituminous or brown coal distillates which
typically have a boiling range of from 150 to 400.degree. C. The
heating oils may be standard heating oil according to DIN 51603-1,
which has a sulfur content of from 0.005 to 0.2% by weight, or they
are low-sulfur heating oils having a sulfur content of from 0 to
0.005% by weight. Examples of heating oil include in particular
heating oil for domestic oil-fired boilers or EL heating oil. The
quality requirements for such heating oils are laid down, for
example, in DIN 51603-1 (cf. also Ullmann's Encyclopedia of
Industrial Chemistry, 5th edition, Volume A12, p. 617 ff., which is
hereby explicitly incorporated by reference).
[0148] The diesel fuels are, for example, crude oil raffinates
which typically have a boiling range from 100 to 400.degree. C.
These are usually distillates having a 95% point up to 360.degree.
C. or even higher. They may also be so-called "ultra low sulfur
diesel" or "city diesel", characterized by a 95% point of, for
example, not more than 345.degree. C. and a sulfur content of not
more than 0.005% by weight, or by a 95% point of, for example,
285.degree. C. and a sulfur content of not more than 0.001% by
weight. In addition to the diesel fuels obtainable by refining
crude oil, suitable diesel fuels also include those obtainable by
coal gasification or gas liquefaction ["gas-to-liquid" ("GTL")
fuels] or by biomass liquefaction ["biomass-to-liquid" ("BTL")
fuels]. Also suitable are mixtures of the aforementioned diesel
fuels with renewable fuels such as biodiesel or bioethanol.
[0149] The diesel fuels are more preferably those having a low
sulfur content, i.e. having a sulfur content of less than 0.05% by
weight, preferably of less than 0.02% by weight, in particular of
less than 0.005% by weight and especially of less than 0.001% by
weight of sulfur.
[0150] Biodiesel (also referred to as biofuel oil) preferably
comprises essentially alkyl esters of fatty acids which derive from
vegetable and/or animal oils and/or fats. Alkyl esters are
understood to mean typically lower alkyl esters, especially
C.sub.1- to C.sub.4-alkyl esters, which are obtainable by
transesterifiying the glycerides which occur in vegetable and/or
animal oils and/or fats, especially triglycerides, by means of
lower alcohols, for example ethanol, n-propanol, isopropanol,
n-butanol, isobutanol, sec-butanol, tert-butanol or especially
methanol ("FAME": fatty acid methyl esters).
[0151] The examples of vegetable oils which are converted to
corresponding alkyl esters and can thus serve as the basis for
biodiesel are castor oil, olive oil, peanut oil, palm kernel oil,
coconut oil, mustard oil, cottonseed oil and especially sunflower
oil, palm oil, soybean oil and rapeseed oil. Further examples
include oils which can be obtained from wheat, jute, sesame and the
shea tree nut; it is also possible to use arachis oil, jatropha oil
and linseed oil.
[0152] It is also possible to convert vegetable oils which have
already been used, for example used deep fat fryer oil, if
appropriate after appropriate cleaning, to alkyl esters and hence
for them to serve as the basis for biodiesel.
[0153] Vegetable fats are likewise usable in principle as a source
for biodiesel, but are of minor importance.
[0154] Examples of animal fats and oils which are converted to
corresponding alkyl esters and can thus serve as the basis for
biodiesel are fish oil, bovine tallow, porcine tallow and similar
fats and oils obtained as wastes in the slaughter or utilization of
farm animals or wild animals.
[0155] The parent saturated or unsaturated fatty acids of the
vegetable and/or animal oils and/or fats mentioned, said fatty
acids usually having from 12 to 22 carbon atoms and possibly
bearing additional functional groups such as hydroxyl groups, which
occur in the alkyl esters are especially lauric acid, myristic
acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
linolenic acid, elaidic acid, erucic acid and ricinoleic acid,
especially in the form of mixtures of such fatty acids.
[0156] Typical lower alkyl esters based on vegetable and/or animal
oils and/or fats which find use as biodiesel or biodiesel
components are, for example, sunflower methyl ester, palm oil
methyl ester ("PME"), soybean oil methyl ester ("SME") and
especially rapeseed oil methyl ester ("RME").
[0157] However, it is also possible to use the monoglycerides,
diglycerides and especially triglycerides themselves, for example
castor oil, or mixtures of such glycerides as biodiesel or
components for biodiesel.
[0158] The present invention also provides additive concentrates
suitable for additizing fuel oil compositions which consist
predominantly of a middle distillate fuel which boils in the range
of 120-500.degree. C. and/or a renewable fuel, said additive
concentrate comprising at least one solubilizer of the general
formula I
##STR00005##
in which [0159] R.sup.1 denotes a hydrocarbylene radical having
from 1 to 12 carbon atoms or a hydrocarbylene radical which has
from 2 to 12 carbon atoms, is interrupted by one or more
heteroatoms selected from the group of O, S and N, and may in each
case bear one or more functional groups selected from the group of
OH, OR.sup.3, NH.sub.2, NHR.sup.4, NR.sup.4R.sup.5, COOH,
COOR.sup.7, CONHR.sup.4 and CONR.sup.4R.sup.5, where amino groups
may also be present in protonated form and carboxylic acid groups
also in deprotonated form,
[0160] X is OH, OR.sup.3, NH.sub.2, NHR.sup.4 or NR.sup.4R.sup.5,
where, in the case that X together with the adjacent carbonyl group
is a carboxylic acid radical, this radical is present in
deprotonated form and the accompanying cation may be a
hydrocarbyl-substituted ammonium cation selected from the group of
[H.sub.3NR.sup.8].sup.+, [H.sub.2NR.sup.8R.sup.9].sup.+ and
[HNR.sup.8R.sup.9R.sup.10].sup.+, [0161] Y is O, S, NH or NR.sup.6,
or, in the case that X is NH.sub.2 or NHR.sup.4, is a chemical bond
to X with formation of an imide structure,
[0162] where R.sup.2 to R.sup.10 are each independently hydrocarbyl
radicals having from 1 to 30 carbon atoms,
[0163] with the proviso that at least one of the R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 radicals has at least 4
carbon atoms,
[0164] in an amount of from 1.05 to 15% by weight, based on the
total amount of the additive concentrate, and [0165] (A) at least
one cold flow improver, [0166] (B) at least one detergent additive
and [0167] (C) an inert organic solvent or a mixture of such
solvents.
[0168] The additive concentrates mentioned preferably additionally
comprise [0169] (D) at least one cetane number improver.
[0170] In a preferred embodiment, the inventive additive
concentrates comprise [0171] (A) from 1 to 50% by weight,
especially from 2 to 40% by weight, in particular from 3 to 20% by
weight, of at least one cold flow improver, [0172] (B) from 0.5 to
40% by weight, preferably from 0.7 to 20% by weight, especially
from 1 to 12% by weight, in particular from 1.5 to 7% by weight, of
at least one detergent additive, [0173] (C) from 1 to 60% by
weight, especially from 3 to 50% by weight, in particular from 5 to
40% by weight, of an inert organic solvent or of a mixture of such
solvents and [0174] (D) from 0 to 80% by weight, especially from 25
to 75% by weight, in particular from 40 to 70% by weight, of at
least one cetane number improver.
[0175] The additive concentrates mentioned may additionally
comprise further ingredients, in which case the sum of all
ingredients adds up to 100% by weight.
[0176] The solubilizers of the general formula I used in accordance
with the invention ensure sufficient homogenization of additive
concentrates which comprise both cold flow improvers and detergent
additives, and also inert organic solvents and if appropriate
cetane number improvers, by stabilizing them such that no flaky
precipitates or opacity occur in the course of formulation or
storage - even in the course of storage over prolonged periods, for
example over several weeks - of the additive concentrates. The
examples which follow are intended to illustrate this effect of the
solubilizers 1.
APPLICATION EXAMPLES
[0177] Additive concentrates composed of the following components
were prepared by mixing:
TABLE-US-00001 Solubilizer L1: Monoamide formed from maleic acid
and tridecylamine (isomer mixture with <50 mol % of
n-tridecylamine) [HOOC--CH.dbd.CH--CO--NH--C.sub.13H.sub.27]
Solubilizer L2: Monoamide formed from succinic acid and
tridecylamine (isomer mixture with <50 mol % of n-tridecylamine)
[HOOC--CH.sub.2--CH.sub.2--CO--NH--C.sub.13H.sub.27] Solubilizer
L3: Monoamide formed from n-decylsuccinic acid and tridecylamine
(isomer mixture with <50 mol % of n-tridecylamine)
[HOOC--CH(C.sub.10H.sub.21)--CH.sub.2--CO--NH--C.sub.13H.sub.27]
Cold flow improver A1: Commercial reaction product formed from 1
mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated
ditallow fat amine [cold flow improver of group (Ad), especially
effective as a paraffin dispersant ("WASA")] Cold flow improver A2:
Commercial ethylene-vinyl acetate-acrylate copolymer [cold flow
improver of group (Aa)] Detergent additive B1: Commercial
polyisobutylenesuccinamide based on an aliphatic polyamine
[detergent component with the (Bh) moiety] Solvent C1: Solvent
Naphtha (Solvesso .RTM. 150) Cetane number improver D1:
2-Ethylhexyl nitrate Deicing agent E1: Ethylene glycol monomethyl
ether Booster F1: Customary oleic acid-diethylenetriamine reaction
product
[0178] The degree of homogenization of the additive concentrates
prepared was assessed visually by the following rating scale:
[0179] Rating 1=no precipitate, clear solution [0180] Rating 2=no
precipitate, slight turbidity, translucent [0181] Rating 3=no
precipitate, high opacity [0182] Rating 4=flaky precipitates,
dispersed [0183] Rating 5=flaky precipitates, settled [0184] Rating
6=severe precipitates, sedimented, or solution gelated
[0185] The compositions of the additive concentrate prepared and
the assessment of their degree of homogenization according to the
above rating scale is evident from the table below (the composition
of the additive concentrates is reported in each case in % by
weight). In all cases, L1 or at least the majority of L1 was added
as the last component. The state of the additive concentrates thus
prepared which was rated remained stable in each case for a
prolonged period.
TABLE-US-00002 TABLE Rating of the degree of homogenization of
additive concentrates Example L1 L2 L3 A1 A2 B1 C1 D1 E1 F1 Rating
1 (for 1.0 0 0 4.3 0 3.0 60 30.9 0 0.8 6 compar- ison) 2
(inventive) 3.0 0 0 4.3 0 3.0 60 28.9 0 0.8 1 3 (for 1.0 0 0 4.3 0
3.0 60 20.9 10 0.8 5** compar- ison) 4 (inventive) 6.0 0 0 4.3 0
3.0 60 15.9 10 0.8 1* 5 (for 1.0 0 0 4.3 7.2 3.0 60 13.7 10 0.8 4-5
compar- ison) 6 (inventive) 4.0 0 0 4.3 7.2 3.0 60 10.7 10 0.8 3 7
(inventive) 1.0 3.0 0 4.3 0 3.0 60 17.9 10 0.8 1* 8 (inventive) 1.0
0 3.0 4.3 0 3.0 60 17.9 10 0.8 1* *Rating immediately after mixing
and constant after storage at 25.degree. C. for 4 weeks **Rating
immediately after mixing: 2, after 1 h: 4, after 3 days: 4, after 4
weeks: 5
* * * * *