U.S. patent application number 13/781929 was filed with the patent office on 2013-09-12 for use of substituted ureas or urethanes for further improvement of the cold flow properties of mineral oils and crude oils.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Ivette GARCIA CASTRO, Wolfgang GRABARSE, Karl HAEBERLE, Markus HANSCH, Bernhard LANGE, Stephan SCHENK, Michael SCHROERS, Jan STRITTMATTER, Irene TROETSCH-SCHALLER.
Application Number | 20130232858 13/781929 |
Document ID | / |
Family ID | 49112769 |
Filed Date | 2013-09-12 |
United States Patent
Application |
20130232858 |
Kind Code |
A1 |
STRITTMATTER; Jan ; et
al. |
September 12, 2013 |
USE OF SUBSTITUTED UREAS OR URETHANES FOR FURTHER IMPROVEMENT OF
THE COLD FLOW PROPERTIES OF MINERAL OILS AND CRUDE OILS
Abstract
The use of substituted monoureas, diureas, polyureas,
monourethanes, bisurethanes or polyurethanes of the formula
R.sup.1X--CO--NR.sup.3R.sup.4 in which X is R.sup.2N or O and
R.sup.1 to R.sup.4 are each independently hydrogen, alkyl radicals,
alkenyl radicals, cycloalkyl radicals, aryl radicals or arylalkyl
radicals, where at least one variable must comprise 4 carbon atoms
and where the urea or urethane functionality may be replicated via
bridging members, for further improvement of the cold flow
properties of mineral oils and crude oils which already comprise
further organic compounds suitable for dispersion or for promoting
dispersion of paraffin crystals which precipitate under cold
conditions, and organic compounds which improve the cold flow
characteristics of mineral oils and crude oils.
Inventors: |
STRITTMATTER; Jan;
(Shanghai, CN) ; HAEBERLE; Karl; (Speyer, DE)
; GRABARSE; Wolfgang; (Mannheim, DE) ; GARCIA
CASTRO; Ivette; (Ludwigshafen, DE) ; HANSCH;
Markus; (Speyer, DE) ; TROETSCH-SCHALLER; Irene;
(Bissersheim, DE) ; SCHENK; Stephan; (Speyer,
DE) ; SCHROERS; Michael; (Bad Duerkheim, DE) ;
LANGE; Bernhard; (Worms, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
49112769 |
Appl. No.: |
13/781929 |
Filed: |
March 1, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61607620 |
Mar 7, 2012 |
|
|
|
Current U.S.
Class: |
44/387 ;
44/417 |
Current CPC
Class: |
C10L 1/2227 20130101;
C10L 1/224 20130101; C10L 2270/026 20130101; C10L 10/14
20130101 |
Class at
Publication: |
44/387 ;
44/417 |
International
Class: |
C10L 1/222 20060101
C10L001/222 |
Claims
1. The use of (i) substituted ureas or urethanes of the general
formula (I) R.sup.1X--CO--NR.sup.3R.sup.4 (I) in which the variable
X is R.sup.2N or O and the variables R.sup.1 to R.sup.4 are each
independently hydrogen, C.sub.1- to C.sub.30-alkyl radicals which
may be interrupted by one or more oxygen atoms, C.sub.3- to
C.sub.30-alkenyl radicals, C.sub.5- to C.sub.30-cycloalkyl
radicals, C.sub.6- to C.sub.30-aryl radicals or C.sub.7- to
C.sub.30-arylalkyl radicals, where at least one of the variables
R.sup.1 to R.sup.4 must be a radical having at least 4 carbon atoms
and where one or more of the variables R.sup.1 to R.sup.4 may be a
radical of the formula (Ia)
-A-(X'--CO-A').sub.n-X'--CO--NR.sup.6R.sup.7 (Ia) in which the
variables A and A' are each an aliphatic, cycloaliphatic, aromatic
or aliphatic-aromatic bridging element having 1 to 20 carbon atoms,
the variable X' is NR.sup.5 or O, the variable n is an integer from
0 to 50 and the variables R.sup.5, R.sup.6 and R.sup.7 are each
independently hydrogen, C.sub.1- to C.sub.30-alkyl radicals which
may be interrupted by one or more oxygen atoms, C.sub.3- to
C.sub.30-alkenyl radicals, C.sub.5- to C.sub.30-cycloalkyl
radicals, C.sub.6- to C.sub.30-aryl radicals or C.sub.7- to
C.sub.30-arylalkyl radicals, where one or more of the variables
R.sup.5 to R.sup.7 may be a radical having at least 4 carbon atoms,
for further improvement of the cold flow properties of mineral oils
and crude oils which already comprise (ii) at least one further
organic compound which is different than (i) and is suitable for
dispersion or for promoting dispersion of paraffin crystals which
precipitate under cold conditions and (iii) at least one organic
compound which is different than (i) and (ii) and improves the cold
flow characteristics of mineral oils and crude oils.
2. The use of substituted ureas or urethanes of the general formula
(I) according to claim 1, in which the variables R.sup.1 to R.sup.4
are each independently hydrogen, C.sub.1- to C.sub.30-alkyl
radicals which may be interrupted by one or more oxygen atoms,
C.sub.3- to C.sub.30-alkenyl radicals, C.sub.5- to
C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl radicals or
C.sub.7- to C.sub.30-arylalkyl radicals, where at least one of the
variables R.sup.1 to R.sup.4 must be a radical having at least 4
carbon atoms.
3. The use of substituted ureas or urethanes of the general formula
(I) according to claim 2, in which the variables R.sup.1 and
R.sup.3 are each hydrogen and the variables R.sup.2 and R.sup.4 are
each the same C.sub.4- to C.sub.30-alkyl radical which may be
interrupted by one or more oxygen atoms, C.sub.4- to
C.sub.30-alkenyl radical, C.sub.5- to C.sub.30-cycloalkyl radical,
C.sub.6- to C.sub.30-aryl radical or C.sub.7- to C.sub.30-arylalkyl
radical.
4. The use of substituted ureas or urethanes of the general formula
(I) according to claim 2, in which the variables R.sup.1 to R.sup.4
are each the same C.sub.4- to C.sub.30-alkyl radical which may be
interrupted by one or more oxygen atoms, C.sub.4- to
C.sub.30-alkenyl radical, C.sub.5- to C.sub.30-cycloalkyl radical,
C.sub.6- to C.sub.30-aryl radical or C.sub.7- to C.sub.30-arylalkyl
radical.
5. The use of substituted ureas or urethanes of the general formula
(I) according to claim 1, in which the variables R.sup.1 to R.sup.4
are each independently hydrogen, C.sub.1- to C.sub.30-alkyl
radicals which may be interrupted by one or more oxygen atoms,
C.sub.3- to C.sub.30-alkenyl radicals, C.sub.5- to
C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl radicals or
C.sub.7- to C.sub.30-arylalkyl radicals, where at least one of the
variables R.sup.1 to R.sup.4 must be a radical having at least 4
carbon atoms, and where at least one other of the variables R.sup.1
to R.sup.4 must be a radical of the formula (Ia) in which the
variables A and A' are each an aliphatic, cycloaliphatic, aromatic
or aliphatic-aromatic bridging element having 1 to 20 carbon atoms
and the variables R.sup.5, R.sup.6 and R.sup.7 are each
independently hydrogen, C.sub.1- to C.sub.30-alkyl radicals which
may be interrupted by one or more oxygen atoms, C.sub.3- to
C.sub.30-alkenyl radicals, C.sub.5- to C.sub.30-cycloalkyl
radicals, C.sub.6- to C.sub.30-aryl radicals or C.sub.7- to
C.sub.30-arylalkyl radicals, where one or more of the variables
R.sup.5 to R.sup.7 may be a radical having at least 4 carbon
atoms.
6. The use of substituted ureas or urethanes of the general formula
(I) according to claim 1 or 5, in which the variable A in the
formula (Ia) is 3,5,5-trimethylcyclohexan-1-ylene-3-methylene,
1,6-hexamethylene, 2,4-tolylene, 2,6-tolylene,
dicyclohexylmethan-4,4'-ylene or diphenylmethan-4,4'-ylene.
7. The use of substituted ureas or urethanes of the general formula
(I) according to claim 5 or 6, in which the variable X is R.sup.2N
where R.sup.2 is a radical of the formula (Ia) in which the
variable n is 0, the variables R.sup.1, R.sup.3, R.sup.5 and
R.sup.7 are each hydrogen and the variables R.sup.4 and R.sup.6 are
each the same C.sub.4- to C.sub.30-alkyl radical which may be
interrupted by one or more oxygen atoms, C.sub.4- to
C.sub.30-alkenyl radical, C.sub.5- to C.sub.30-cycloalkyl radical,
C.sub.6- to C.sub.30-aryl radical or C.sub.7- to C.sub.30-arylalkyl
radical.
8. The use of substituted ureas or urethanes of the general formula
(I) according to claims 1 to 7, wherein the mineral oils or crude
oils comprise at least one polar nitrogen compound as component
(ii).
9. The use of substituted ureas or urethanes of the general formula
(I) according to claims 1 to 8, wherein the mineral oils or crude
oils comprise, as component (iii), at least one copolymer of a
C.sub.2- to C.sub.40-olefin with at least one further ethylenically
unsaturated monomer.
10. A mixture comprising (i) 1 to 99% by weight of at least one
substituted urea or substituted urethane of the general formula (I)
according to claims 1 to 7, (ii) 1 to 50% by weight of at least one
further organic compound which is different than (i) and is
suitable for dispersion or for promoting dispersion of paraffin
crystals which precipitate under cold conditions and (iii) 1 to 99%
by weight of at least one organic compound which is different than
(i) and (ii) and improves the cold flow characteristics of mineral
oils and crude oils, where the sum of all components (i) to (iii)
adds up to 100% by weight.
11. A fuel, especially middle distillate fuel, comprising a mixture
according to claim 10.
12. The fuel according to claim 11, comprising, as further
additives in amounts customary therefor, conductivity improvers,
anticorrosion additives, lubricity additives, antioxidants, metal
deactivators, antifoams, demulsifiers, detergents, cetane number
improvers, solvents or diluents, dyes or fragrances or mixtures
thereof.
13. A fuel additive concentrate comprising 10 to 70% by weight,
based on the total amount of the concentrate, of a mixture
according to claim 10, dissolved in a hydrocarbon solvent.
14. The fuel additive concentrate according to claim 13,
comprising, as further additives in amounts customary therefor,
conductivity improvers, anticorrosion additives, lubricity
additives, antioxidants, metal deactivators, antifoams,
demulsifiers, detergents, cetane number improvers, solvents or
diluents, dyes or fragrances or mixtures thereof.
Description
[0001] The present invention relates to the use of particular
substituted ureas or urethanes for further improvement of the cold
flow properties of mineral oils and crude oils, especially middle
distillate fuels, which already comprise organic compounds suitable
for dispersion or for promoting dispersion of paraffin crystals
which precipitate under cold conditions, and organic compounds
which improve the cold flow characteristics of mineral oils and
crude oils, especially middle distillate fuels.
[0002] The invention further relates to a mixture which comprises
the substituted ureas or urethanes mentioned and already comprises
organic compounds suitable for dispersion or for promoting
dispersion of paraffin crystals which precipitate under cold
conditions out of mineral oils and crude oils, especially middle
distillate fuels, and organic compounds which improve the cold flow
characteristics of mineral oils and crude oils, especially middle
distillate fuels. The present invention further relates to fuels
and fuel additive concentrates which comprise this mixture.
[0003] Middle distillate fuels of fossil origin, especially gas
oils, diesel oils or light heating oils, which are obtained from
mineral oil, have different contents of paraffins depending on the
origin of the crude oil. At low temperatures, there is
precipitation of solid paraffins at the cloud point ("CP"). In the
course of further cooling, the platelet-shaped n-paraffin crystals
form a kind of "house of cards structure" and the middle distillate
fuel ceases to flow even though its predominant portion is still
liquid. The precipitated n-paraffins in the temperature range
between cloud point and pour point ("PP") considerably impair the
flowability of the middle distillate fuels; the paraffins block
filters and cause irregular or completely interrupted fuel supply
to the combustion units. Similar disruptions occur in the case of
light heating oils.
[0004] It has long been known that suitable additives can modify
the crystal growth of the n-paraffins in middle distillate fuels.
Very effective additives prevent middle distillate fuels from
solidifying even at temperatures a few degrees Celsius below the
temperature at which the first paraffin crystals crystallize out.
Instead, fine, readily crystallizing, separate paraffin crystals
are formed, which, even when the temperature is lowered further,
pass through filters in motor vehicles and heating systems, or at
least form a filtercake which is permeable to the liquid portion of
the middle distillates, so that disruption-free operation is
ensured. The effectiveness of the flow improvers is typically
expressed, in accordance with European standard EN 116, indirectly
by measuring the cold filter plugging point ("CFPP"). Cold flow
improvers or middle distillate flow improvers ("MDFIs") of this
kind which are used include, for example, ethylene-vinyl
carboxylate copolymers such as ethylene-vinyl acetate copolymers
("EVA").
[0005] One disadvantage of these additives is that the paraffin
crystals modified in this way, owing to their higher density
compared to the liquid portion, tend to settle out more and more at
the bottom of the vessel in the course of storage of the middle
distillate fuel. As a result, a homogeneous low-paraffin phase
forms in the upper part of the vessel, and a biphasic paraffin-rich
layer at the bottom. Since the fuel is usually drawn off just above
the vessel bottom both in vehicle fuel tanks and in storage or
supply tanks of mineral oil dealers, there is the risk that the
high concentration of solid paraffins leads to blockages of filters
and metering devices. The further the storage temperature is below
the precipitation temperature of the paraffins, the greater this
risk becomes, since the amount of paraffin precipitated increases
with falling temperature. In particular, fractions of biodiesel
also enhance this undesired tendency of the middle distillate fuel
to paraffin sedimentation.
[0006] By virtue of the additional use of paraffin dispersants or
wax antisettling additives ("WASAs"), the problems outlined can be
reduced.
[0007] In view of declining world mineral oil reserves and the
discussion surrounding the environmentally damaging consequences of
the consumption of fossil and mineral fuels, interest is rising in
the additional use of alternative energy sources based on renewable
raw materials. These include in particular native oils and fats of
vegetable or animal origin. These are in particular triglycerides
of fatty acids having from 10 to 24 carbon atoms, which are
converted to lower alkyl esters such as methyl esters. These esters
are generally also referred to as "FAMEs" (fatty acid methyl
esters).
[0008] As is the case for middle distillates of mineral or fossil
origin, crystals which can likewise block motor vehicle filters and
metering devices precipitate out in the course of cooling of such
FAMEs. However, these crystals do not consist of n-paraffins but
rather of fatty acid esters; in spite of this, it is possible to
characterize fuels based on FAMEs with the same parameters as for
the middle distillates of fossil origin (CP, PP, CFPP).
[0009] Said mixtures of these FAMEs with middle distillates
generally have poorer cold performance than middle distillates of
fossil or mineral origin alone. In the case of mixtures with middle
distillates of fossil origin, the addition of the FAMEs increases
the tendency to form paraffin sediments. In particular, however,
the FAMEs mentioned, when they are intended to partly replace
middle distillates of fossil origin as biofuel oils, have
excessively high CFPP values, such that they cannot be used without
difficulty as a fuel or heating oil according to the current
country- and region-specific requirements. The increase in the
viscosity in the course of cooling also influences the cold
properties in FAMEs to a greater extent than in pure middle
distillates of fossil or mineral origin.
[0010] There have already been proposals of additives which are
intended to improve the cold properties of fuels. For instance,
U.S. Pat. No. 2,657,984, published Nov. 3, 1953, recommends
substituted ureas and substituted urethanes for lowering the pour
point in fuel oils. The lowering described therein of the PP values
in the fuel oil, however, is only a few .degree. F. and was
determined in the absence of further additives.
[0011] Japanese patent application JP-A S56-93796, published Jul.
29, 1981, describes the combination of (A) urea or biuret
derivatives of polyisocyanates and relatively long-chain
dialkylamines and (B) ethylene-vinyl acetate copolymers as flow
improvers for fuel oils. Such flow improvers modify wax crystals in
fuel oils in such a way that the flow characteristics of the fuel
oil at low temperatures is improved. The radicals on the relatively
long-chain dialkylamines mentioned may have 1 to 26 carbon atoms
and be linear or branched. Examples of urea or biuret derivatives
(A) are the reaction products of di(n-octadecyl)amine or
di(dodecyl)amine and toluene diisocyanate, hexamethylene
diisocyanate, diphenylmethane 4,4'-diisocyanate,
trimethylolpropane/toluene 2,4-diisocyanate (Desmodur.RTM. TH) or
trimeric hexamethylene diisocyanate (Sumidur.RTM. N75).
[0012] It was an object of the present invention to provide
products which bring about improved cold flow characteristics in
mineral oils and crude oils, especially in middle distillate fuels.
More particularly, the CFPP for such fuels was to be lowered in a
more effective manner.
[0013] The object is achieved in accordance with the invention by
the use of (i) substituted ureas or urethanes of the general
formula (I)
R.sup.1X--CO--NR.sup.3R.sup.4 (I)
[0014] in which the variable X is R.sup.2N or O and the variables
R.sup.1 to R.sup.4 are each independently hydrogen, C.sub.1- to
C.sub.30-alkyl radicals which may be interrupted by one or more
oxygen atoms, C.sub.3- to C.sub.30-alkenyl radicals, C.sub.5- to
C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl radicals or
C.sub.7- to C.sub.30-arylalkyl radicals, where at least one of the
variables R.sup.1 to R.sup.4 must be a radical having at least 4
carbon atoms and where one or more of the variables R.sup.1 to
R.sup.4 may be a radical of the formula (Ia)
-A-(X'--CO-A').sub.n-X'--CO--NR.sup.6R.sup.7 (Ia)
[0015] in which the variables A and A' are each an aliphatic,
cycloaliphatic, aromatic or aliphatic-aromatic bridging element
having 1 to 20 carbon atoms, the variable X' is NR.sup.5 or O, the
variable n is an integer from 0 to 50 and the variables R.sup.5,
R.sup.6 and R.sup.7 are each independently hydrogen, C.sub.1- to
C.sub.30-alkyl radicals which may be interrupted by one or more
oxygen atoms, C.sub.3- to C.sub.30-alkenyl radicals, C.sub.5- to
C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl radicals or
C.sub.7- to C.sub.30-arylalkyl radicals, where one or more of the
variables R.sup.5 to R.sup.7 may be a radical having at least 4
carbon atoms,
[0016] for further improvement of the cold flow properties of
mineral oils and crude oils which already comprise [0017] (ii) at
least one further organic compound which is different than (i) and
is suitable for dispersion or for promoting dispersion of paraffin
crystals which precipitate under cold conditions and [0018] (iii)
at least one organic compound which is different than (i) and (ii)
and improves the cold flow characteristics of mineral oils and
crude oils.
[0019] Mineral oils in the context of the present invention are
understood to mean the oils produced by distillation from brown
coal, hard coal, peat, wood, mineral oil and other mineral or
fossil raw materials suitable for this purpose, in refineries and
similar production operations. In contrast to fats and fatty oils
such as FAME, these mineral oils consist predominantly or
exclusively of paraffinic, naphthenic and aromatic hydrocarbons.
These oils may additionally also comprise alkenes (olefins), and
amounts of sulfur-containing and nitrogen-containing organic
compounds which vary according to provenance.
[0020] Mineral oils in the context of the present invention are
additionally understood to mean all upgraded tradable products
produced from these mineral oils by further purification steps such
as fractional distillation or catalytic hydrogenation, or by
addition of further components or of additives, more particularly
fuels, fuel oils, heating oils, lubricants or operating fluids. Of
particular interest in this context are fuels such as gasoline
fuels (gasoline) and especially middle distillate fuels such as
diesel fuels and turbine fuels (jet fuel), and also heating
oils.
[0021] Crude oils are understood in the context of the present
invention to mean mineral oils which have not been treated any
further, from which mineral oils are produced by distillation after
the production and transport thereof, for example by pipeline or by
ship, from the production sites to the refineries.
[0022] The inventive interaction of components (i), (ii) and (iii)
in mineral oils and crude oils improves the cold flow
characteristics in the course of transport thereof, for example
through pipes, pipelines and lines, and in the course of storage
thereof, for example in storage tanks. Further positive effects
which are brought about as a result are better handling, for
example better filterability.
[0023] The substituted ureas and urethanes of the general formula
(I) are monoureas (X.dbd.NR.sup.2) or monourethanes (X.dbd.O) in
the case that they do not comprise any radical of the formula (Ia),
diureas (X.dbd.X'.dbd.NR.sup.2) or bisurethanes (X.dbd.X'.dbd.O) in
the case that they comprise a radical of the formula (Ia) where
n=0, and polyureas (X.dbd.X'.dbd.NR.sup.2) or polyurethanes
(X.dbd.X'.dbd.O) in the case that they comprise a radical of the
formula (Ia) where n>0. The compounds (I) may also comprise a
plurality of, for example two, three or four, radicals of the
formula (Ia). It is also possible to use mixed urea/urethane
compounds (I) with one or more radicals of the formula (Ia) in
which the individual variables X and X' may be either NR.sup.2 or
O.
[0024] Possible C.sub.1- to C.sub.30-alkyl radicals for R.sup.1 to
R.sup.7 are preferably linear or branched alkyl radicals, for
example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl,
2-ethylhexyl, neooctyl, nonyl, neononyl, isononyl, decyl, neodecyl,
2-propylheptyl, undecyl, neoundecyl, dodecyl, tridecyl,
isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, tricosyl and
the constitution isomers thereof.
[0025] Alkyl radicals interrupted by one or more oxygen atoms for
R.sup.1 to R.sup.7 having up to 30 carbon atoms are, for example,
radicals of the formula --(CHR.sup.8--CH.sub.2--O).sub.m--R.sup.9
in which the variable R.sup.8 is hydrogen, a C.sub.1- to
C.sub.4-alkyl radical such as methyl, ethyl or n-propyl, or phenyl,
the variable R.sup.9 is as defined for the variables R.sup.1 to
R.sup.7, but especially hydrogen or linear or branched C.sub.1- to
C.sub.20-alkyl, and the variable m is an integer from 1 to 30.
Individual examples of such radicals are
--(CH.sub.2--CH.sub.2--O).sub.m--R.sup.9 where m=1 to 15,
--[CH(CH.sub.3)--CH.sub.2--O].sub.m--R.sup.9 where m=1 to 25,
--[CH(C.sub.2H.sub.5)--CH.sub.2--O].sub.m--R.sup.9 where m=1 to 25
and --(CHPh--CH.sub.2--O).sub.m--R.sup.9 where m=1 to 4, where
R.sup.9 in each case is hydrogen, methyl, ethyl, 2-ethylhexyl,
2-propylheptyl or isotridecyl.
[0026] Possible C.sub.3- to C.sub.30-alkenyl radicals for R.sup.1
to R.sup.7 are, for example, linear alkenyl radicals such as allyl,
oleyl, linolyl and linolenyl.
[0027] Relatively long-chain linear alkyl radicals and alkenyl
radicals may also be of natural origin and may originate, for
example, from mono-, di- and/or triglycerides in oils or fats such
as sunflower oil, palm (kernel) oil, soybean oil, rapeseed oil,
castor oil, olive oil, peanut oil, coconut oil, mustard oil,
linseed oil, cotton seed oil or tallow fat; such alkyl radicals of
natural origin are generally mixtures of homologous species or
species of similar chain length.
[0028] Possible C.sub.5- to C.sub.30-cycloalkyl radicals for
R.sup.1 to R.sup.7 are preferably C.sub.5- to C.sub.10-cycloalkyl
radicals, for example cyclopentyl, cyclohexyl, 2-, 3- or
4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or
3,5-dimethylcyclohexyl, cycloheptyl and cyclooctyl.
[0029] Possible C.sub.6- to C.sub.30-aryl radicals for R.sup.1 to
R.sup.7 are preferably C.sub.6- to C.sub.10-aryl radicals, for
example phenyl, naphthyl, tolyl and o-, m- or p-xylyl.
[0030] Possible C.sub.7- to C.sub.30-arylalkyl radicals for R.sup.1
to R.sup.7 are preferably C.sub.7- to C.sub.10-arylalkyl radicals,
for example benzyl, 2-phenylethyl, 3-phenylpropyl and
4-phenylbutyl.
[0031] The alkyl, alkenyl, cycloalkyl, aryl and arylalkyl radicals
mentioned may comprise, to a small extent, functional groups such
as hydroxyl groups or carboxylic ester groups, without destroying
the predominant hydrocarbon character of the moiety.
[0032] At least one of the variables R.sup.1 to R.sup.4 and
optionally one or more of the variables R.sup.5 to R.sup.7 has 4 or
more, preferably 8 to 30 and in particular 12 to 24 carbon atoms,
in order to ensure sufficient oil solubility. The remaining
variables R.sup.1 to R.sup.7 in that case are generally short-chain
and are, for example, C.sub.1- to C.sub.4-alkyl radicals, or are
hydrogen.
[0033] The variables A and A' denote bridging elements in diureas,
bisurethanes, polyureas and polyurethanes. In the case of polyureas
and polyurethanes, A and A' may be different or preferably the
same. Typical bridging elements A or A' are: polymethylene moieties
of the formula --(CH.sub.2).sub.p-- where p=1 to 20, especially p=2
to 10, in particular p=3 to 6; C.sub.5- to C.sub.10-cycloalkylene
groups such as 1,2-, 1,3- or 1,4-cyclohexylene, the radical of
1,2-, 1,3- or 1,4-dimethylcyclohexane which is bifunctional on the
side chains, the bifunctional radical of the isophorone skeleton,
or the radical of dicyclohexylmethane which is bifunctional on the
cyclohexane rings; C.sub.6- to C.sub.10-arylene groups such as
1,2-, 1,3- or 1,4-phenylene; C.sub.8- to C.sub.14-alkylarylene
moieties such as the aromatic bifunctional radical of
diphenylmethane; arylenealkylene moieties having 8 to 14 carbon
atoms, such as the aliphatic bifunctional radical of o-, m- or
p-xylene.
[0034] In a preferred embodiment, use is made of substituted ureas
or urethanes of the general formula (I), in which the variable A in
the formula (Ia) is 3,5,5-trimethylcyclohexan-1-ylene-3-methylene
(derived from the isophorone skeleton), 1,6-hexamethylene,
2,4-tolylene, 2,6-tolylene, dicyclohexylmethan-4,4'-ylene or
diphenylmethan-4,4'-ylene.
[0035] The variable n denotes, in the case of polyureas and
polyurethanes, an integer from 1 to 50, preferably 2 to 25,
especially 3 to 20 and in particular 4 to 10.
[0036] In a preferred embodiment, use is made of substituted ureas
or urethanes of the general formula (I), in which the variables
R.sup.1 to R.sup.4 are each independently hydrogen, C.sub.1- to
C.sub.30-alkyl radicals which may be interrupted by one or more
oxygen atoms, C.sub.3- to C.sub.30-alkenyl radicals, C.sub.5- to
C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl radicals or
C.sub.7- to C.sub.30-arylalkyl radicals, where at least one of the
variables R.sup.1 to R.sup.4 must be a radical having at least 4
carbon atoms. The compounds (I) of this embodiment do not comprise
any radicals of the formula (Ia) and are thus monoureas or
monourethanes.
[0037] In a further preferred embodiment, the monoureas or
monourethanes used are substituted ureas or urethanes of the
general formula (I), in which the variables R.sup.1 and R.sup.3 are
each hydrogen and the variables R.sup.2 and R.sup.4 are each the
same C.sub.4- to C.sub.30-alkyl radical which may be interrupted by
one or more oxygen atoms, C.sub.4- to C.sub.30-alkenyl radical,
C.sub.5- to C.sub.30-cycloalkyl radical, C.sub.6- to C.sub.30-aryl
radical or C.sub.7- to C.sub.30-arylalkyl radical.
[0038] In a further preferred embodiment, the monoureas or
monourethanes used are substituted ureas or urethanes of the
general formula (I), in which the variables R.sup.1 to R.sup.4 are
each the same C.sub.4- to C.sub.30-alkyl radical which may be
interrupted by one or more oxygen atoms, C.sub.4- to
C.sub.30-alkenyl radical, C.sub.5- to C.sub.30-cycloalkyl radical,
C.sub.6- to C.sub.30-aryl radical or C.sub.7- to C.sub.30-arylalkyl
radical.
[0039] In a further preferred embodiment, use is made of
substituted ureas or urethanes of the general formula (I), in which
the variables R.sup.1 to R.sup.4 are each independently hydrogen,
C.sub.1- to C.sub.30-alkyl radicals which may be interrupted by one
or more oxygen atoms, C.sub.3- to C.sub.30-alkenyl radicals,
C.sub.5- to C.sub.30-cycloalkyl radicals, C.sub.6- to C.sub.30-aryl
radicals or C.sub.7- to C.sub.30-arylalkyl radicals, where at least
one of the variables R.sup.1 to R.sup.4 must be a radical having at
least 4 carbon atoms, and where at least one other of the variables
R.sup.1 to R.sup.4 must be a radical of the formula (Ia) in which
the variables A and A' are each an aliphatic, cycloaliphatic,
aromatic or aliphatic-aromatic bridging element having 1 to 20
carbon atoms and the variables R.sup.5, R.sup.6 and R.sup.7 are
each independently hydrogen, C.sub.1- to C.sub.30-alkyl radicals
which may be interrupted by one or more oxygen atoms, C.sub.3- to
C.sub.30-alkenyl radicals, C.sub.5- to C.sub.30-cycloalkyl
radicals, C.sub.6- to C.sub.30-aryl radicals or C.sub.7- to
C.sub.30-arylalkyl radicals, where one or more of the variables
R.sup.5 to R.sup.7 may be a radical having at least 4 carbon atoms.
The compounds (I) of this embodiment comprise radicals of the
formula (Ia) and are thus diureas, bisurethanes, polyureas or
polyurethanes.
[0040] In a further preferred embodiment, use is made of
substituted ureas or urethanes of the general formula (I), in which
the variable X is R.sup.2N where R.sup.2 is a radical of the
formula (Ia) in which the variable n is 0, the variables R.sup.1,
R.sup.3, R.sup.5 and R.sup.7 are each hydrogen and the variables
R.sup.4 and R.sup.6 are each the same C.sub.4- to C.sub.30-alkyl
radical which may be interrupted by one or more oxygen atoms,
C.sub.4- to C.sub.30-alkenyl radical, C.sub.5- to
C.sub.30-cycloalkyl radical, C.sub.6- to C.sub.30-aryl radical or
C.sub.7- to C.sub.30-arylalkyl radical. The compounds (I) of this
embodiment are thus diureas.
[0041] Typical examples of usable monoureas and monourethanes of
the general formula (I) are N,N'-di(2-ethylhexyl)urea,
N,N'-di(2-propylheptyl)urea, N,N'-di(isotridecyl)urea,
N,N'-di(tetradecyl)urea, N,N'-di(hexadecyl)urea,
N,N'-di(octadecyl)urea, N,N'-dioleylurea, N,N'-diphenylurea,
N,N,N',N'-tetra(n-butyl)urea, N,N,N',N'-tetra(2-ethylhexyl)urea,
N,N,N',N'-tetra(2-propylheptyl)urea,
N,N,N',N'-tetra(isotridecyl)urea, N,N,N',N'-tetra(tetradecyl)urea,
N,N,N',N'-tetra(hexadecyl)urea, N,N,N',N'-tetra(octadecyl)urea,
N,N,N',N'-tetraoleylurea, N,N,N',N'-tetraphenylurea,
N-phenyl-2-ethylhexylurethane, N-phenyl-2-propylheptylurethane,
N-phenylisotridecylurethane, N-phenyltetradecylurethane,
N-phenylhexadecylurethane, N-phenyloctadecylurethane and
N-phenyloleylurethane.
[0042] Typical examples of usable diureas and bisurethanes of the
general formula (I) are the isophorone-derived compounds of the
formula (II)
##STR00001##
[0043] with the following variable definitions:
[0044] (IIa) R.sup.12.dbd.R.sup.15.dbd.H,
R.sup.10.dbd.R.sup.11.dbd.R.sup.13.dbd.R.sup.14=n-butyl,
[0045] (IIb) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=2-ethylhexyl,
[0046] (IIc) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=2-propylheptyl,
[0047] (IId) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-decyl,
[0048] (IIe) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-dodecyl,
[0049] (IIf) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-tridecyl,
[0050] (IIg) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=isotridecyl,
[0051] (IIh) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-tetradecyl,
[0052] (IIj) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-hexadecyl,
[0053] (IIk) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=n-octadecyl,
[0054] (IIm) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=oleyl,
[0055] (IIn) R.sup.11.dbd.R.sup.12.dbd.R.sup.14.dbd.R.sup.15.dbd.H,
R.sup.13.dbd.R.sup.14=phenyl,
[0056] and the diureas which are analogous to the compounds (IIa)
to (IIn) and have the same R.sup.10 to R.sup.15 radicals and have,
as bridging element A, a 1,6-hexamethylene, 2,4-tolylene,
2,6-tolylene or diphenylmethan-4,4'-ylene skeleton; and
additionally isophorone-derived compounds of the formula (III)
##STR00002##
[0057] with the following variable definitions:
[0058] (IIIa) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-butyl,
[0059] (IIIb) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=2-ethylhexyl,
[0060] (IIIc) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=2-propylheptyl,
[0061] (IIId) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-decyl,
[0062] (IIIe) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-dodecyl,
[0063] (IIIf) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-tridecyl,
[0064] (IIIg) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=isotridecyl,
[0065] (IIIh) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-tetradecyl,
[0066] (IIIj) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-hexadecyl,
[0067] (IIIk) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=n-octadecyl,
[0068] (IIIm) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=oleyl,
[0069] (IIIn) R.sup.17.dbd.R.sup.19.dbd.H,
R.sup.16.dbd.R.sup.18=phenyl,
[0070] and the bisurethanes which are analogous to the compounds
(IIIa) to (IIIn) and have the same R.sup.16 to R.sup.19 radicals
and have, as bridging element A, a 1,6-hexamethylene, 2,4-tolylene,
2,6-tolylene or diphenylmethan-4,4'-ylene skeleton.
[0071] Typical examples of usable polyureas and polyurethanes of
the general formula (I) are the reaction product of 1 mol of
isophorone diisocyanate with a mixture of 0.5 to 1 mol of
tridecylamine and 0.5 to 0.75 mol of isophoronediamine to give a
polyurea, and the reaction product of 1 mol of isophorone
diisocyanate with a mixture of 0.5 to 1 mol of tridecanol and 0.5
to 0.75 mol of hexane-1,6-diol to give a polyurethane.
[0072] The monoureas, monourethanes, diureas, bisurethanes,
polyureas and polyurethane of the general formula (I) are known as
such from the prior art and the person skilled in the art is
familiar with the options for preparing them. Standard preparation
methods for the compounds (I) are based on the reactions of
isocyanates with appropriate mono- or polyamines and/or appropriate
mono- or polyfunctional alcohols.
[0073] Useful isocyanates include, as well as monoisocyanates such
as phenyl isocyanate, the polyisocyanates typically used in
polyurethane chemistry, for example aliphatic, aromatic and
cycloaliphatic di- and polyisocyanates with hydrocarbyl radicals of
corresponding chain length or size and with an NCO functionality of
at least 1.8, especially 1.8 to 5 and in particular 2 to 4, and
isocyanurates, biurets, allophanates and uretdiones thereof.
[0074] Examples of customary diisocyanates are: aliphatic and
araliphatic diisocyanates such as tetramethylene diisocyanate,
hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene
diisocyanate, decamethylene diisocyanate, dodecamethylene
diisocyanate, tetradecamethylene diisocyanate, esters of lysine
diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane
diisocyanate or tetramethylhexane diisocyanate; cycloaliphatic
diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane,
the trans/trans, cis/cis and cis/trans isomers of 4,4'- or
2,4'-di(isocyanatocyclohexyl)methane,
1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane
(isophorone diisocyanate), 2,2-bis(4-isocyanatocyclohexyl)propane,
1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or 2,4- or
2,6-diisocyanato-1-methylcyclohexane; aromatic diisocyanates such
as tolylene 2,4- or 2,6-diisocyanate and the isomer mixtures
thereof, o-, m- or p-xylylene diisocyanate, 2,4'- or
4,4'-diisocyanatodiphenylmethane and the isomer mixtures thereof,
phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene
2,4-diisocyanate, naphthylene 1,5-diisocyanate, diphenylene
4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl,
3-methyldiphenylmethane 4,4'-diisocyanate, 1,4-diisocyanatobenzene
or diphenyl ether 4,4'-diisocyanate. It is also possible to use
mixtures of the diisocyanates mentioned.
[0075] Useful polyisocyanates are also polyisocyanates having
isocyanurate groups, uretdione diisocyanates, polyisocyanates
having biuret groups, polyisocyanates having urethane or
allophanate groups, polyisocyanates comprising oxadiazinetrione
groups, uretonimine-modified polyisocyanates of linear or branched
C.sub.4-C.sub.20-alkylene diisocyanates, cycloaliphatic
diisocyanates having a total of 6 to 20 carbon atoms or aromatic
diisocyanates having a total of 8 to 20 carbon atoms, or mixtures
thereof.
[0076] The usable di- and polyisocyanates preferably have a content
of isocyanate groups (calculated as NCO, molecular weight=42
daltons) of 10 to 60% by weight, based on the di- and
polyisocyanate (mixture), especially 15 to 60% by weight and in
particular 20 to 55% by weight.
[0077] Further useful polyisocyanates include: [0078] 1.
Isocyanurate group-containing polyisocyanates of aromatic,
aliphatic, araliphatic and/or cycloaliphatic diisocyanates. Of
particular interest here are the corresponding aliphatic and/or
cycloaliphatic isocyanato isocyanurates and especially those based
on hexamethylene diisocyanate and isophorone diisocyanate. The
present isocyanurates are especially tris(isocyanatoalkyl) or
tris(isocyanatocycloalkyl) isocyanurates, which are cyclic trimers
of the diisocyanates, or mixtures with the higher homologs thereof
having more than one isocyanurate ring. The isocyanato
isocyanurates generally have an NCO content of 10 to 30% by weight,
especially 15 to 25% by weight, and a mean NCO functionality of 3
to 4.5. [0079] 2. Uretdione diisocyanates having aromatically,
aliphatically, araliphatically and/or cycloaliphatically bonded
isocyanate groups, preferably aliphatically and/or
cycloaliphatically bonded, and especially those derived from
hexamethylene diisocyanate or isophorone diisocyanate. Uretdione
diisocyanates are cyclic dimerization products of diisocyanates.
The uretdione diisocyanates can be used in the formulations as the
sole component or in a mixture with other polyisocyanates,
especially those mentioned under 1. [0080] 3. Biuret
group-containing polyisocyanates with aromatically,
cycloaliphatically, aliphatically or araliphatically bonded,
preferably cycloaliphatically or aliphatically bonded, isocyanate
groups, especially tris(6-isocyanatohexyl)biuret or mixtures
thereof with higher homologs thereof. These polyisocyanates having
biuret groups generally have an NCO content of 18 to 22% by weight
and a mean NCO functionality of 3 to 4.5. [0081] 4. Urethane and/or
allophanate group-containing polyisocyanates having aromatically,
aliphatically, araliphatically or cycloaliphatically bonded,
preferably aliphatically or cycloaliphatically bonded, isocyanate
groups, as obtainable, for example, by reaction of excess amounts
of hexamethylene diisocyanate or of isophorone diisocyanate with
polyhydric alcohols, for example trimethylolpropane, neopentyl
glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol,
1,3-propanediol, ethylene glycol, diethylene glycol, glycerol,
1,2-dihydroxypropane or mixtures thereof. These polyisocyanates
having urethane and/or allophanate groups generally have an NCO
content of 12 to 20% by weight and a mean NCO functionality of 2.5
to 3. [0082] 5. Oxadiazinetrione group-comprising polyisocyanates,
preferably derived from hexamethylene diisocyanate or isophorone
diisocyanate. Such polyisocyanates comprising oxadiazinetrione
groups are preparable from diisocyanate and carbon dioxide. [0083]
6. Uretoneimine-modified polyisocyanates.
[0084] The polyisocyanates mentioned above under points 1. to 6.
can be used in a mixture with one another, or else optionally in a
mixture with diisocyanates.
[0085] Important mixtures of these isocyanates are especially the
mixtures of the respective structural isomers of
diisocyanatotoluene and diisocyanatodiphenylmethane; a mixture of
particular interest is that of 20 mol % of 2,4-diisocyanatotoluene
and 80 mol % of 2,6-diisocyanatotoluene. Further particularly
advantageous mixtures are those of aromatic isocyanates such as
2,4-diisocyanatotoluene and/or 2,6-diisocyanatotoluene with
aliphatic or cycloaliphatic isocyanates such as hexamethylene
diisocyanate or isophorone diisocyanate, the preferred mixing ratio
of the aliphatic to aromatic isocyanates being 4:1 to 1:4. Also of
significance are polycyclic diphenylmethane diisocyanate and
uretonimine-containing diphenylmethane diisocyanate (Lupranat.RTM.
MM 103).
[0086] It is also possible to use isocyanates which, as well as the
free isocyanate groups, bear further capped isocyanate groups, for
example uretdione or urethane groups.
[0087] The monoamines which can be reacted with the mono-, di- and
polyisocyanates mentioned to give urea systems typically bear a
primary or secondary amino group. Of particular interest in this
context are monoalkylamines and dialkylamines, especially those
with at least one relatively long-chain alkyl radical, for example
having at least 4, especially at least 8 and in particular at least
12 carbon atoms. Examples of such monoamines are n-butylamine,
n-butylmethylamine, n-butylethylamine, n-butyl-n-propylamine,
di(n-butyl)amine, n-pentylamine, neopentylamine, n-hexylamine,
cyclohexylamine, dicyclohexylamine, n-heptylamine, n-octylamine,
di(n-octyl)amine, neooctylamine, 2-ethylhexylamine,
di(2-ethylhexylamine), n-nonylamine, neononylamine,
2-propylheptylamine, di(2-propylheptyl)amine, n-undecylamine,
neoundecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine,
di(isotridecyl)amine, n-tetradecylamine, n-pentadecylamine,
n-hexadecylamine, n-heptadecylamine, n-octadecylamine, oleylamine,
linolylamine, linolenylamine, n-nonadecylamine, eicosylamine,
heneicosylamine, tricosylamine and the constitutional isomers
thereof. The alkyl chains in these amines may also be interrupted
by one or more oxygen atoms or by one or more tertiary nitrogen
atoms, as in 2-methoxyethylamine, 3-methoxypropylamine,
3-ethoxypropylamine, 3-(2-ethylhexoxy)propylamine,
di(2-methoxyethyl)amine, or in analogous or similar relatively
long-chain polyetheramines and in 2-(diethylamino)ethylamine or
2-(diisopropylamino)ethylamine. In addition, it is also possible,
for example, to use aromatic and araliphatic amines such as
aniline, N-methylaniline, N-ethylaniline,
N-(2-hydroxyethyl)aniline, diphenylamine, 2,6-xylidine, o-, m- or
p-toluidine, .alpha.- or .beta.-naphthylamine, 1-phenylethylamine
and 2-phenylethylamine. A further example of a usable primary or
secondary monoamine is N-(3-aminopropyl)imidazole (Lupragen.RTM.
API).
[0088] Di- and polyamines which can be reacted with the mono-, di-
and polyisocyanates mentioned to give urea systems are generally
polyfunctional amines having a molecular weight of 32 to 500 and
especially of 60 to 300, which comprise at least two primary or two
secondary amino groups or one primary and one secondary amino
group. Examples thereof are diamines such as 1,2-diaminoethane,
1,2-diaminopropane, 1,3-diaminopropane, diaminobutanes such as
1,4-diaminobutane, diaminopentanes such as 1,5-diaminopentane or
neopentanediamine, diaminohexanes such as 1,6-diaminohexane,
diaminooctanes such as 1,8-diaminooctane, piperazine,
2,5-dimethylpiperazine,
amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine),
4,4'-diaminodicyclohexylmethane,
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane,
1,4-diaminocyclohexane, 4,4'-methylenedianiline,
aminoethylethanolamine, hydrazine, hydrazine hydrate, or triamines
such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane, or
higher amines such as triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, or polymeric amines such as
polyethyleneamines, hydrogenated polyacrylonitriles or at least
partly hydrolyzed poly-N-vinylformamides, each having a molecular
weight of up to 2000 daltons, especially up to 1000 daltons. The
alkyl chains in these amines may also be interrupted by one or more
oxygen atoms or by one or more tertiary nitrogen atoms, as in
4,7,10-trioxatridecane-1,13-diamine,
4,9-dioxadodecane-1,12-diamine, or in analogous or similar
relatively long-chain polyetheramines, for example in aminated
ethylene glycol polyethers or glyceryl polyethers, and in
N,N-bis(3-aminopropyl)-methylamine.
[0089] Examples of alcohols which can be reacted with the mono-,
di- and polyisocyanates mentioned to give urethane systems are
monools, especially alkanols, such as methanol, ethanol,
isopropanol, n-propanol, isopropanol, n-butanol, isobutanol,
sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol,
tert-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol,
n-nonanol, n-decanol, 2-propylheptanol, n-undecanol, n-dodecanol
(lauryl alcohol), n-tridecanol, isotridecanol, n-tetradecanol,
n-hexadecanol, n-octadecanol, oleyl alcohol, n-eicosanol,
n-heneicosanol, n-tricosanol and ethoxylates and propoxylates of
the monools mentioned. Further suitable monools are ethylene glycol
monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol
monomethyl ether, and ethoxylates and propoxylates of long-chain
amines and carboxamides, such as coconut fatty amine, oleylamine or
oleamide. Further suitable monools are 1-ethynyl-1-cyclohexanol,
2-mercaptoethanol, 2-methyl-3-butyn-2-ol, 3-butyn-2-ol,
4-ethyl-1-octyn-3-ol, ethylenechlorohydrin, propargyl alcohol,
dimethylaminoethoxyethanol (Lupragen.RTM. N107),
dimethylethanolamine (Lupragen.RTM. N101) and
trimethylaminoethylethanolamine (Lupragen.RTM. N400). Further
suitable monools are derivatives of glycerol and trimethylolpropane
in which 2 of the 3 hydroxyl groups have been derivatized, for
example glyceryl distearate or glyceryl dioleate.
[0090] Further examples of alcohols which can be reacted with the
mono-, di- and polyisocyanates mentioned to give urethane systems
are diols and polyols which may have low molecular weights of
typically 50 to 500 daltons, especially 60 to 200 daltons, or high
molecular weights of typically 500 to 5000 daltons, especially 1000
to 3000 daltons.
[0091] Examples of low molecular weight diols of this kind are
ethylene glycol, propane-1,2-diol, propane-1,3-diol,
butane-1,3-diol, butane-2,3-diol, but-2-ene-1,4-diol,
but-2-yne-1,4-diol, pentane-1,2-diol, pentane-1,5-diol, neopentyl
glycol, hex-3-yne-2,5-diol, bis(hydroxymethyl)cyclohexanes such as
1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol,
2,5-dimethyl-2,5-hexanediol, 2,2'-thiobisethanol, hydroxypivalic
acid neopentyl glycol ester, diisopropanol-p-toluidine,
N,N-di(2-hydroxyethyl)aniline, diethanolamine, dipropanolamine,
diisopropanolamine, and also diethylene glycol, triethylene glycol,
tetraethylene glycol, polyethylene glycols, dipropylene glycol,
polypropylene glycols, dibutylene glycol and polybutylene glycols.
Also suitable are derivatives of triols such as glycerol and
trimethylolpropane which are present in monosubstituted form, e.g.
glyceryl monooleate. Of particular interest are neopentyl glycol,
and alcohols of the general formula HO--(CH.sub.2).sub.x--OH where
x is a number from 1 to 20, especially an even number from 2 to 20.
Examples thereof are 1,2-ethylene glycol, butane-1,4-diol,
hexane-1,6-diol, octane-1,8-diol, decane-1,10-diol and
dodecane-1,12-diol.
[0092] The low molecular weight diols mentioned are also used as
formation components for the preparation of the polyester polyols
listed below, preference being given here to the unbranched diols
having 2 to 12 carbon atoms and an even number of carbon atoms, and
also to pentanediol-1,5 and neopentyl glycol.
[0093] Alcohols having a higher functionality than 2, especially
having 3 hydroxyl groups, which may serve to establish a certain
degree of branching or crosslinking, are, for example,
trimethylolbutane, trimethylolpropane, trimethylolethane,
pentaerythritol, glycerol, triethanolamine, tripropanolamine,
triisopropanolamine, sugar alcohols such as sorbitol, mannitol,
diglycerol, threitol, erythritol, adonitol (ribitol), arabitol
(lyxitol), xylitol, dulcitol (galactitol), maltitol or isomalt, and
also sugars.
[0094] Additionally useful here are also monoalcohols which, as
well as the hydroxyl group, bear a further group reactive toward
isocyanates, especially amino alcohols such as monoalcohols having
one or more primary and/or secondary amino groups, for example
monoethanolamine, 3-amino-1-propanol, 5-amino-1-pentanol,
3-dimethylaminopropan-1-ol, 1-(2-hydroxyethyl)piperazine,
4-(2-hydroxyethyl)morpholine, 2-(2-aminoethoxy)ethanol,
N-methyldiethanolamine, N-butylethanolamine,
N,N-dibutylethanolamine, N,N-diethylethanolamine,
N,N-dimethylethanolamine, butyldiethanolamine, N-ethylethanolamine,
N,N-dimethylisopropanolamine, N-methylethanolamine, diethanolamine,
Isopropanolamine, N-(2-hydroxyethyl)aniline and
N-(2-aminoethyl)ethanolamine.
[0095] Examples of higher molecular weight diols and polyols are
firstly polyester polyols. Of particular interest are polyester
polyols which are obtained by reaction of the abovementioned low
molecular weight diols with dibasic carboxylic acids. Instead of
the free polycarboxylic acids, it is also possible to use the
corresponding polycarboxylic anhydrides or corresponding
polycarboxylic esters of lower alcohols or mixtures thereof to
prepare the polyester polyols. The polycarboxylic acids may be
aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic,
and may optionally be substituted, for example by halogen atoms,
and/or unsaturated. Examples of usable dibasic carboxylic acids or
derivatives thereof include: suberic acid, azelaic acid, phthalic
acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic
anhydride, hexahydrophthalic anhydride, tetrachlorophthalic
anhydride, endomethylenetetrahydrophthalic anhydride, glutaric
anhydride, maleic acid, maleic anhydride, fumaric acid, and also
dimeric fatty acids. Preference is given to dicarboxylic acids of
the formula HOOC--(CH.sub.2).sub.y--COOH in which y is a number
from 1 to 20, especially an even number from 2 to 20, e.g. succinic
acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
[0096] Further useful higher molecular weight diols are also
polycarbonate diols, as obtainable, for example, by reaction of
phosgene with an excess of the low molecular weight diols mentioned
as formation components for the polyester polyols.
[0097] Suitable higher molecular weight diols are also
lactone-based polyester diols, which are homo- or copolymers of
lactones, especially terminal hydroxyl group-containing addition
products of lactones onto suitable difunctional starter molecules.
Useful lactones preferably include those derived from
hydroxycarboxylic acids of the general formula
HO--(CH.sub.2).sub.z--COOH in which z is a number from 1 to 20,
especially an odd number from 3 to 19, for example
.epsilon.-caprolactone, .beta.-propiolactone, .gamma.-butyrolactone
and/or methyl-.epsilon.-caprolactone, and mixtures thereof.
Suitable starter components are, for example, the low molecular
weight diols mentioned above as formation components for the
polyesterpolyols. The corresponding polymers of
.epsilon.-caprolactone are of particular interest. It is also
possible to use lower molecular weight polyester diols or polyether
diols as starters for preparation of the lactone polymers. Instead
of the polymers of lactones, it is also possible to use the
corresponding chemically equivalent polycondensates of the
hydroxycarboxylic acids corresponding to the lactones.
[0098] In addition, useful higher molecular weight diols are also
polyether diols. They are obtainable especially by polymerization
of ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofuran, styrene oxide or epichlorohydrin with themselves,
for example in the presence of BF.sub.3, or by addition of these
compounds, optionally in a mixture or in succession, onto start
components with reactive hydrogen atoms such as alcohols or amines,
for example water, ethylene glycol, propane-1,2-diol,
propane-1,3-diol, 2,2-bis(4-hydroxydiphenyl)propane or aniline. Of
particular interest is polytetrahydrofuran having a molecular
weight of 250 to 5000, and in particular 1000 to 4500.
[0099] The polyester diols and polyether diols mentioned can also
be used as mixtures in a ratio of 0.1:1 to 1:9.
[0100] The conditions for the reaction of the isocyanates mentioned
with the mono- or polyamines mentioned and/or the mono- or
polyfunctional alcohols mentioned are likewise familiar to the
person skilled in the art. For instance, the polyaddition of the
isocyanates onto the amines or alcohols is effected generally at
reaction temperatures of 20 to 180.degree. C., especially of 50 to
150.degree. C., and under standard pressure. The reaction times
required may extend over a few minutes to a few hours. The person
skilled in the art in the field of polyurethane chemistry knows how
the reaction time can be influenced by a multitude of parameters
such as temperature, concentration of the monomers or reactivity of
the monomers.
[0101] To accelerate the reaction of the isocyanates, the customary
catalysts can be used in addition. Useful catalysts for this
purpose in principle include all of those used customarily in
polyurethane chemistry. These are, for example, organic amines,
especially tertiary aliphatic, cycloaliphatic or aromatic amines,
and/or Lewis acidic organic metal compounds. Examples of useful
Lewis-acidic organic metal compounds include, for example, tin
compounds, for example tin(II) salts of organic carboxylic acids,
e.g. tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and
tin(II) laurate, and the dialkyltin(IV) salts of organic carboxylic
acids, e.g. dimethyltin diacetate, dibutyltin diacetate, dibutyltin
dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate,
dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate.
Metal complexes such as acetylacetonates of iron, titanium,
aluminum, zirconium, manganese, nickel and cobalt are also
possible, for example zirconium acetylacetonate and zirconium
2,2,6,6-tetramethyl-3,5-heptanedionate. In addition, it is also
possible to use bismuth and cobalt catalysts and cesium salts as
catalysts, for example cesium carboxylates.
[0102] The reaction of the isocyanates mentioned with the mono- or
polyamines mentioned and/or the mono- or polyfunctional alcohols
mentioned can be performed in the presence or absence of solvents.
Examples of suitable solvents are aprotic solvents such as
open-chain or cyclic carbonates, lactones, di(cyclo)alkyl
dipropylene glycol ethers, N-(cyclo)alkylcaprolactams,
N-(cyclo)alkylpyrrolidones, ketones, hydrocarbons and amides.
[0103] Useful polymerization apparatuses for the reaction of the
isocyanates mentioned with the mono- or polyamines mentioned and/or
the mono- or polyfunctional alcohols mentioned include stirred
tanks, especially when additional use of solvents ensures a low
viscosity and good heat removal. If the reaction is performed in
substance, extruders are particularly suitable due to the usually
high viscosities and the usually only short reaction times,
especially self-cleaning multiscrew extruders.
[0104] A suitable possible synthesis for monoureas of the general
formula (I), i.e. for compounds of the structure
R.sup.1R.sup.2N--CO--NR.sup.3R.sup.4 without a radical of the
formula (Ia), is the reaction of phosgene, diphosgene or
triphosgene with twice the equivalent amount per COCl.sub.2 unit of
a primary or secondary monoamine. In this case, an inert solvent
such as a halohydrocarbon, e.g. dichloromethane, is employed at
-10.degree. C. to +50.degree. C., especially at +10.degree. C. to
+30.degree. C., and a weak base is added, for example a tertiary
amine, in order to bind the hydrogen chloride formed.
[0105] Component (ii) ensures dispersion on its own or promotes
dispersion of paraffin crystals which precipitate out of the
mineral oils and crude oils under cold conditions. These are wax
antisettling additives (WASAs). In the case of promoting dispersion
of the paraffin crystals, component (ii) enhances the possible
dispersing action of component (i), the substituted ureas or
urethanes.
[0106] In a preferred embodiment, substituted ureas or urethanes of
the general formula (I) are used in mineral oils or crude oils
which comprise at least one polar nitrogen compound as component
(ii).
[0107] Polar nitrogen compounds suitable as component (ii) may be
either ionic or nonionic and preferably have at least one
substituent, especially at least two substituents, in the form of a
tertiary nitrogen atom of the general formula >NR.sup.23 in
which R.sup.23 is a C.sub.8-C.sub.40-hydrocarbyl 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 hydrocarbyl radical
with a carboxylic acid having 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. Primary amines
suitable for preparing the polar nitrogen compounds mentioned are,
for example, n-octylamine, n-nonylamine, n-decylamine,
n-undecylamine, n-dodecylamine, n-tetradecylamine and the higher
linear homologs. Secondary amines suitable for this purpose are,
for example, di-n-octadecylamine and methylbehenylamine. Also
suitable for this purpose 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, cyclohexane-1,2-dicarboxylic acid,
cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic
acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic
acid, terephthalic acid and succinic acids substituted by
long-chain hydrocarbyl radicals.
[0108] Further examples of suitable polar nitrogen compounds are
ring systems which bear at least two substituents of the formula
-A''-NR.sup.24R.sup.25 in which A'' is a linear or branched
aliphatic hydrocarbyl group optionally interrupted by one or more
moieties selected from O, S, NR.sup.36 and CO, and R.sup.24 and
R.sup.25 are each a C.sub.9- to C.sub.40-hydrocarbyl radical
optionally interrupted by one or more moieties selected from O, S,
NR.sup.36 and CO and/or substituted by one or more substituents
selected from OH, SH and NR.sup.36R.sup.37, where R.sup.36 is
C.sub.1- to C.sub.40-alkyl optionally interrupted by one or more
moieties selected from CO, NR.sup.37, O and S and/or substituted by
one or more radicals selected from NR.sup.38R.sup.39, OR.sup.38,
SR.sup.38, COR.sup.38, COOR.sup.38, CONR.sup.38R.sup.39, aryl and
heterocyclyl, where R.sup.38 and R.sup.39 are each independently
selected from H and C.sub.1- to C.sub.4-alkyl and where R.sup.37 is
H or R.sup.36.
[0109] More particularly, component (ii) is an oil-soluble reaction
product of poly(C.sub.2- to C.sub.20-carboxylic acids) having at
least one tertiary amino group with primary or secondary amines.
The poly(C.sub.2- to C.sub.20-carboxylic acids) which have at least
one tertiary amino group and form the basis of this reaction
product comprise preferably at least 3 carboxyl groups, especially
3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic
acid units in the polycarboxylic acids have preferably 2 to 10
carbon atoms, and are especially acetic acid units. The carboxylic
acid units are suitably bonded to the polycarboxylic acids, for
example via one or more carbon and/or nitrogen atoms. They are
preferably attached to tertiary nitrogen atoms which, in the case
of a plurality of nitrogen atoms, are bonded via hydrocarbon
chains.
[0110] Component (ii) is preferably an oil-soluble reaction product
based on poly(C.sub.2- to C.sub.20-carboxylic acids) which have at
least one tertiary amino group and are of the general formula IVa
or IVb
##STR00003##
[0111] in which the variable A* is a straight-chain or branched
C.sub.2- to C.sub.6-alkylene group or the moiety of the formula
V
##STR00004##
[0112] and the variable B is a C.sub.1- to C.sub.19-alkylene
group.
[0113] Moreover, the preferred oil-soluble reaction product of
component (ii), especially that of the general formula IVa or IVb,
is an amide, an amide-ammonium salt or an ammonium salt in which
no, one or more carboxylic acid groups have been converted to amide
groups.
[0114] Straight-chain or branched C.sub.2- to C.sub.6-alkylene
groups of the variable A* are, for example, 1,1-ethylene,
1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene,
1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene,
2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene
(hexamethylene) and in particular 1,2-ethylene. The variable A*
comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.
[0115] C.sub.1- to C.sub.19-alkylene groups of the variable B are
before, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene,
hexamethylene, octamethylene, decamethylene, dodecamethylene,
tetradecamethylene, hexadecamethylene, octadecamethylene,
nonadecamethylene and especially methylene. The variable B
comprises preferably 1 to 10 and especially 1 to 4 carbon
atoms.
[0116] The primary and secondary amines as a reaction partner for
the polycarboxylic acids to form component (ii) are typically
monoamines, especially aliphatic monoamines. These primary and
secondary amines may be selected from a multitude of amines which
bear hydrocarbyl radicals optionally joined to one another.
[0117] These amines underlying the oil-soluble reaction products of
component (ii) are preferably secondary amines and have the general
formula HN(R*).sub.2 in which the two variables R* are each
independently straight-chain or branched C.sub.10- to
C.sub.30-alkyl radicals, especially C.sub.14- to C.sub.24-alkyl
radicals. These relatively long-chain alkyl radicals are preferably
straight-chain or only slightly branched. In general, the secondary
amines mentioned, with regard to their relatively long-chain alkyl
radicals, derive from naturally occurring fatty acids or from
derivatives thereof. The two R* radicals are preferably
identical.
[0118] The secondary amines mentioned may be bonded to the
polycarboxylic acids by means of amide structures or in the form of
the ammonium salts; it is also possible for only a portion to be
present as amide structures and another portion as ammonium salts.
Preferably only few, if any, free acid groups are present. In a
preferred embodiment, the oil-soluble reaction products of
component (ii) are present completely in the form of the amide
structures.
[0119] Typical examples of such components (ii) are reaction
products of nitrilotriacetic acid, of ethylenediaminetetraacetic
acid or of propylene-1,2-diaminetetraacetic acid with in each case
0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per
carboxyl group, of dioleylamine, dipalmitinamine, dicocoamine,
distearylamine, dibehenylamine or especially ditallowamine. A
particularly preferred component (ii) is the reaction product of 1
mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated
ditallowamine.
[0120] Further typical examples of component (ii) include the
N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for
example the reaction product of 1 mol of phthalic anhydride and 2
mol of ditallowamine, the latter being hydrogenated or
unhydrogenated, and the reaction product of 1 mol of an
alkenylspirobislactone with 2 mol of a dialkylamine, for example
ditallowamine and/or tallowamine, the last two being hydrogenated
or unhydrogenated.
[0121] Further typical examples of component (ii) include
monoamides of dicarboxylic acids, which by reaction of dicarboxylic
acids or reactive dicarboxylic acid derivatives, such as anhydrides
thereof, with primary or secondary amines having straight-chain or
branched C.sub.10 to C.sub.30 alkyl radicals mentioned, for example
the reaction product of 1 mol of maleic anhydride with 1 mol of a
long-chain primary amine such as isotridecylamine.
[0122] Further typical structure types for the component of class
(ii) are cyclic compounds with tertiary amino groups or condensates
of long-chain primary or secondary amines with carboxylic
acid-containing polymers, as described in WO 93/18115.
[0123] For component (ii), it is also possible to use mixtures of
various species, for example a mixture of an oil-soluble reaction
product based on poly(C.sub.2- to C.sub.20-carboxylic acids) which
have at least one tertiary amino group and are of the general
formula IVa or IVb with a monoamide of a dicarboxylic acid.
[0124] For component (iii), it is possible in principle to use any
organic compounds which are capable of improving the cold flow
characteristics of mineral oils and crude oils. For the intended
purpose, they must have sufficient oil solubility. Especially
suitable for this purpose are cold flow improvers (MDFIs) typically
used in the case of middle distillates of mineral or fossil origin,
i.e. in the case of conventional diesel fuels and heating oils.
However, it is also possible to use, as component (iii), organic
compounds which, when used in conventional diesel fuels and heating
oils, partly or predominantly have the properties of a wax
antisettling additive (WASA). They also partly or predominantly act
as nucleators.
[0125] More particularly, component (iii), which generally
represents a different substance class than component (ii), is
selected from the following classes: [0126] (f1) copolymers of a
C.sub.2- to C.sub.40-olefin with at least one further ethylenically
unsaturated monomer; [0127] (f2) comb polymers; [0128] (f3)
polyoxyalkylenes; [0129] (f4) polar nitrogen compounds; [0130] (f5)
sulfocarboxylic acids or sulfonic acids or derivatives thereof; and
[0131] (f6) poly(meth)acrylic esters.
[0132] It is possible to use either mixtures of different
representatives from one of the particular classes (f1) to (f6) or
mixtures of representatives from different classes (f1) to (f6).
When (f4) polar nitrogen compounds are used as component (iii),
component (ii) is generally not such a polar nitrogen compound.
[0133] In a preferred embodiment, substituted ureas or urethanes of
the general formula (I) are used in mineral oils or crude oils
which comprise, as component (iii), at least one (f1) copolymer of
a C.sub.2- to C.sub.40-olefin with at least one further
ethylenically unsaturated monomer.
[0134] Suitable C.sub.2- to C.sub.40-olefin monomers for the
copolymers (f1) are, for example, those having 2 to 20 and
especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2
carbon-carbon double bonds, especially 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, more preferably
.alpha.-olefins having 2 to 6 carbon atoms, for example propene,
1-butene, 1-pentene, 1-hexene and in particular ethylene.
[0135] In the copolymers (f1), the at least one further
ethylenically unsaturated monomer is preferably selected from
alkenyl carboxylates, (meth)acrylic esters and further olefins.
When further olefins are also copolymerized, they are preferably
higher in molecular weight than the abovementioned C.sub.2- to
C.sub.40-olefin base monomer. When, for example, the olefin base
monomer used is ethylene or propene, suitable further olefins are
especially C.sub.10- to C.sub.40-.alpha.-olefins. Further olefins
are in most cases only additionally copolymerized when monomers
with carboxylic ester functions are also used.
[0136] Suitable (meth)acrylic esters are, for example, esters of
(meth)acrylic acid with C.sub.1- to C.sub.20-alkanols, especially
C.sub.1- to C.sub.10-alkanols, in particular with methanol,
ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol,
tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol,
nonanol and decanol, and structural isomers thereof.
[0137] Suitable alkenyl carboxylates are, for example, C.sub.2- to
C.sub.14-alkenyl esters, for example the vinyl and propenyl esters,
of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon
radical may be linear or branched. Among these, preference is given
to the vinyl esters. Among the carboxylic acids with a branched
hydrocarbon radical, preference is given to those whose branch is
in the .alpha.-position to the carboxyl group, the .alpha.-carbon
atom more preferably being tertiary, i.e. the carboxylic acid being
a so-called neocarboxylic acid. However, the hydrocarbon radical of
the carboxylic acid is preferably linear.
[0138] Examples of suitable alkenyl carboxylates 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 alkenyl
carboxylate is vinyl acetate; typical copolymers of group (f1)
resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs").
Very particular preference is given to using, as component (f1), at
least one such ethylene-vinyl acetate copolymer. Ethylene-vinyl
acetate copolymers usable particularly advantageously and their
preparation are described in WO 99/29748.
[0139] Suitable copolymers (f1) are also those which comprise two
or more different alkenyl carboxylates in copolymerized form, which
differ in the alkenyl function and/or in the carboxylic acid group.
Likewise suitable are copolymers which, as well as the alkenyl
carboxylate(s), comprise at least one olefin and/or at least one
(meth)acrylic ester in copolymerized form.
[0140] In a further preferred embodiment, (f1) is at least one
terpolymer of a C.sub.2- to C.sub.40-.alpha.-olefin, a C.sub.1- to
C.sub.20-alkyl ester of an ethylenically unsaturated monocarboxylic
acid having 3 to 15 carbon atoms and a C.sub.2- to C.sub.14-alkenyl
ester of a saturated monocarboxylic acid having 2 to 21 carbon
atoms. Terpolymers of this kind are described in WO 2005/054314. A
typical terpolymer of this kind is formed from ethylene,
2-ethylhexyl acrylate and vinyl acetate.
[0141] The or the further ethylenically unsaturated monomer(s) are
copolymerized into the copolymers (f1) in an amount of preferably 1
to 50% by weight, especially 10 to 45% by weight and in particular
20 to 40% by weight, based on the overall copolymer. The main
proportion in terms of weight of the monomer units in the
copolymers (f1) therefore originates generally from the C.sub.2 to
C.sub.40 base olefins.
[0142] The copolymers (f1) preferably have a number-average
molecular weight M.sub.n of 1000 to 20 000 daltons, more preferably
1000 to 10 000 daltons and especially 1000 to 8000 daltons.
[0143] As well as the preferred copolymers of class (f1), is is
also advantageously possible to use the compounds of classes (f2)
to (f6) as component (iii).
[0144] Comb polymers suitable as compounds (f2) are, for example,
those described in WO 2004/035715 and 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). Further
suitable comb polymers (f2) are, for example, those obtainable by
the 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.
Mixtures of comb polymers are also suitable. Comb polymers may also
be polyfumarates or polymaleates. Homo- and copolymers of vinyl
ethers are also suitable comb polymers.
[0145] Polyoxyalkylenes suitable as compounds (f3) are, for
example, polyoxyalkylene esters, ethers, ester/ethers and mixtures
thereof, especially based on polyethylene glycols or polypropylene
glycols. The polyoxyalkylene compounds preferably comprise at least
one linear alkyl group, more preferably at least two linear alkyl
groups, each having 10 to 30 carbon atoms and a polyoxyalkylene
group having a number-average molecular weight of up to 5000
daltons, especially of 100 to 5000 daltons. The alkyl group of the
polyoxyalkylene radical comprises preferably 1 to 4 carbon atoms.
Also of particular interest here are polyoxyalkylene esters and
diesters of fatty acids having 10 to 30 carbon atoms, such as
stearic acid or behenic acid. Such polyoxyalkylene compounds are
described, for example, in EP-A 061 895 and also in U.S. Pat. No.
4,491,455.
[0146] Suitable compounds (f4) are the polar nitrogen compounds
described above under component (ii).
[0147] Suitable compounds (f5) are sulfocarboxylic acids or
sulfonic acids or derivatives thereof, as described, for example,
in EP-A-0 261 957. Such sulfocarboxylic acids or sulfonic acids are
especially the reaction products of 1 mol of ortho-sulfobenzoic
acid or the cyclic anhydride thereof with 2 mol of a long-chain
dialkylamine such as hydrogenated ditallowamine.
[0148] Poly(meth)acrylic esters suitable as compounds (f6) 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 with regard to the esterified
alcohol. If appropriate, the copolymer comprises another different
olefinically unsaturated monomer in copolymerized form. The
weight-average molecular weight of the polymer is preferably 50 000
to 500 000 daltons. A particularly preferred polymer is a copolymer
of methacrylic acid and methacrylic esters of saturated C.sub.14
and C.sub.15 alcohols, the acid groups having been neutralized with
hydrogenated tallamine. Suitable poly(meth)acrylic esters are
described, for example, in WO 00/44857.
[0149] The present invention also provides a mixture comprising
[0150] (i) 1 to 99% by weight, especially 5 to 95% by weight and in
particular 10 to 50% by weight of at least one substituted urea or
substituted urethane of the general formula (I) [0151] (ii) 1 to
50% by weight, especially 3 to 40% by weight and in particular 5 to
30% by weight of at least one further organic compound which is
different than (i) and is suitable for dispersion or for promoting
dispersion of paraffin crystals which precipitate under cold
conditions and [0152] (iii) 1 to 99% by weight, especially 5 to 95%
by weight and in particular 10 to 50% by weight of at least one
organic compound which is different than (i) and (ii) and improves
the cold flow characteristics of mineral oils and crude oils,
[0153] where the sum of all components (i) to (iii) adds up to 100%
by weight.
[0154] The inventive mixture is suitable as an additive to mineral
oils and crude oils, especially to middle distillate fuels, which
may also be mixtures of biofuel oils and middle distillate fuels of
mineral or fossil origin. Their addition serves principally to
improve the cold flow characteristics of these liquids. Middle
distillate fuels of mineral or fossil origin, which find use
especially as gas oils, petroleum, diesel oils (diesel fuels),
turbine fuels, kerosene or (light) heating oils, are often also
referred to as fuel oils. Such middle distillate fuels generally
have boiling points of 120 to 450.degree. C.
[0155] The inventive mixture can be added directly, i.e. in
undiluted form, to the mineral oils and crude oils, especially to
the middle distillate fuels, but is preferably added as a 5 to 90%
by weight, especially as a 10 to 70% by weight and in particular as
a 25 to 60% by weight solution (concentrate) in a suitable solvent,
typically a hydrocarbon solvent. Such a concentrate comprising 5 to
90% by weight, especially 10 to 70% by weight and in particular 25
to 60% by weight, based on the total amount of the concentrate, of
the inventive mixture dissolved in a hydrocarbon solvent therefore
also forms part of the subject matter of the present invention.
Common solvents in this context are aliphatic or aromatic
hydrocarbons, for example xylenes or mixtures of high-boiling
aromatics such as Solvent Naphtha. It is also advantageously
possible here to use low-naphthalene aromatic hydrocarbon mixtures
such as low-naphthalene Solvent Naphtha as solvents. Additionally
suitable for this purpose are also solvents from the group of the
alcohols, esters and ethers, including the polyoxyalkylenes and the
polyglycols, these being soluble in biofuel oils and middle
distillates. It is also possible to use middle distillate fuels
themselves as solvents for such concentrates.
[0156] The dosage of the mixture in the mineral oils and crude
oils, especially in the middle distillate fuels, is generally 10 to
10 000 ppm by weight, especially 50 to 5000 ppm by weight, in
particular 100 to 3000 ppm by weight, for example 500 to 1500 ppm
by weight, based in each case on the total amount of oil or
fuel.
[0157] The inventive mixture can be used as an additive to middle
distillate fuels which consist [0158] (A) to an extent of 0.1 to
100% by weight, preferably to an extent of 0.1 to less than 100% by
weight, especially to an extent of 10 to 95% by weight and in
particular to an extent of 30 to 90% by weight, of at least one
biofuel oil which is based on fatty acid esters, and [0159] (B) to
an extent of 0 to 99.9% by weight, preferably to an extent of more
than 0 to 99.9% by weight, especially to an extent of 5 to 90% by
weight and in particular to an extent of 10 to 70% by weight, of
middle distillates of fossil origin and/or of vegetable and/or
animal origin, which are essentially hydrocarbon mixtures and are
free of fatty acid esters.
[0160] The fuel component (A) is usually also referred to as
"biodiesel". The middle distillates of fuel component (A)
preferably essentially comprise alkyl esters of fatty acids which
derive from vegetable and/or animal oils and/or fats. Alkyl esters
are typically understood to mean lower alkyl esters, especially
C.sub.1- to C.sub.4-alkyl esters, which are obtainable by
transesterifying the glycerides, especially triglycerides, which
occur in vegetable and/or animal oils and/or fats by means of lower
alcohols, for example ethanol, n-propanol, isopropanol, n-butanol,
isobutanol, sec-butanol, tert-butanol or in particular methanol
("FAME").
[0161] Examples of vegetable oils which can be 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
shea tree nut; it is also possible to use arachis oil, jatropha oil
and linseed oil. The extraction of these oils and their conversion
to the alkyl esters are known from the prior art or can be derived
therefrom.
[0162] It is also possible to convert already used vegetable oils,
for example used deep fat fryer oil, optionally after appropriate
cleaning, to alkyl esters and thus for them to serve as the basis
for biodiesel. Vegetable fats can in principle likewise be used as
a source for biodiesel, but play a minor role.
[0163] 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.
[0164] The parent saturated or unsaturated fatty acids of the
vegetable and/or animal oils and/or fats mentioned, which usually
have 12 to 22 carbon atoms and may bear additional functional
groups such as hydroxyl groups, and 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/or ricinoleic acid.
[0165] 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").
[0166] 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.
[0167] In the context of the present invention, the fuel component
(B) shall be understood to mean middle distillate fuels boiling in
the range from 120 to 450.degree. C. Such middle distillate fuels
are used especially as diesel fuel, heating oil or kerosene,
particular preference being given to diesel fuel and heating
oil.
[0168] Middle distillate fuels refer to fuels which are obtained by
distilling crude oil as the first process step and boil within the
range from 120 to 450.degree. C. Preference is given to using
low-sulfur middle distillates, i.e. those which comprise less than
350 ppm of sulfur, especially less than 200 ppm of sulfur, in
particular less than 50 ppm of sulfur. In special cases, they
comprise less than 10 ppm of sulfur; these middle distillates are
also referred to as "sulfur-free". They are generally crude oil
distillates which have been subjected to refining under
hydrogenating conditions and therefore comprise only small
proportions of polyaromatic and polar compounds. They are
preferably those middle distillates which have 90% distillation
points below 370.degree. C., especially below 360.degree. C. and in
special cases below 330.degree. C.
[0169] Low-sulfur and sulfur-free middle distillates may also be
obtained from relatively heavy mineral oil fractions which cannot
be distilled under atmospheric pressure. Typical conversion
processes for preparing middle distillates from heavy crude oil
fractions include: hydrocracking, thermal cracking, catalytic
cracking, coking processes and/or visbreaking. Depending on the
process, these middle distillates are obtained in low-sulfur or
sulfur-free form, or are subjected to refining under hydrogenating
conditions.
[0170] The middle distillates preferably have aromatics contents of
below 28% by weight, especially below 20% by weight. The content of
normal paraffins is between 5% by weight and 50% by weight,
preferably between 10 and 35% by weight.
[0171] The middle distillates referred to as fuel component (B)
shall also be understood here to mean middle distillates which can
either be derived indirectly from fossil sources such as mineral
oil or natural gas, or else are prepared from biomass via
gasification and subsequent hydrogenation. A typical example of a
middle distillate fuel which is derived indirectly from fossil
sources is the GTL ("gas-to-liquid") diesel fuel obtained by means
of Fischer-Tropsch synthesis. A middle distillate is prepared from
biomass, for example via the BTL ("biomass-to-liquid") process, and
can be used either alone or in a mixture with other middle
distillates as fuel component (B). The middle distillates also
include hydrocarbons which are obtained by the hydrogenation of
fats and fatty oils. They comprise predominantly n-paraffins. It is
common to the middle distillate fuels mentioned that they are
essentially hydrocarbon mixtures and are free of fatty acid
esters.
[0172] The qualities of the heating oils and diesel fuels are laid
down in more detail, for example, in DIN 51603 and EN 590 (cf. also
Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume
A12, p. 617 ff., which is hereby incorporated explicitly by
reference).
[0173] The inventive mixture may be added either to pure middle
distillate fuels of mineral or fossil origin or to mixtures thereof
with biofuel oils (biodiesel) to improve their properties. In both
cases, a significant improvement in the cold flow characteristics
of the fuel is observed, i.e. a lowering especially of the CFPP
values, but also the CP values and/or the PP values, irrespective
of the origin or the composition of the fuel. The CFPP values are
determined here--and also in relation to the inventive use of the
substituted ureas and urethanes (i) for further improvement of the
cold flow properties in combination with components (ii) and
(iii)--typically to the standard EN 116, and the CP values
typically to the standard ISO 3015. The crystals which precipitate
out are generally effectively kept suspended, and so there are no
blockages of filters and lines by such sediments. The inventive
mixture in most cases has a good activity spectrum and thus has the
effect that the crystals which precipitate out are dispersed very
efficiently in a wide variety of different fuels.
[0174] Equally, the use of the inventive mixture can improve a
series of further fuel properties. Mention shall be made here by
way of example merely of the additional effect as a corrosion
protectant or the improvement of the oxidation stability.
[0175] The present invention also provides middle distillate fuels,
optionally with a content of biofuel oils (biodiesel).
[0176] In general, the middle distillate fuels mentioned or the
fuel additive concentrates mentioned also comprise, as further
additives in amounts customary therefor, conductivity improvers,
anticorrosion additives, lubricity additives, antioxidants, metal
deactivators, antifoams, demulsifiers, detergents, cetane number
improvers, solvents or diluents, dyes or fragrances or mixtures
thereof. The further additives which have been mentioned above but
have not yet been addressed above, are familiar to those skilled in
the art and therefore need not be explained any further here.
[0177] The examples which follow are intended to illustrate the
present invention without restricting it.
[0178] Abbreviations:
[0179] Ilco-Min 8015 C C.sub.12-C.sub.14 cocoamine technical grade,
equivalent weight 208
[0180] Ilco-Min 8040 T C.sub.16-C.sub.18 tallowamine, partly
unsaturated, equivalent weight 271
[0181] Inipol DS N-tallowalkyl-1,3-propanediamine, equivalent
weight 299
[0182] IPDA isophoronediamine
[0183] IPDI isophorone diisocyanate
[0184] HMDI dicyclohexylmethane 4,4'-diisocyanate
[0185] 4,4'-MDI diphenylmethane 4,4'-diisocyanate
[0186] Solvesso.RTM. 150 aromatic solvent, boiling range
181-207.degree. C.
PREPARATION EXAMPLES 1-6
Diureas from Diisocyanate and Monoamine
[0187] A stirred flask with thermometer and reflux condenser was
initially charged with 160 g of Solvesso.RTM. 150 and the
isocyanate, and the amine was added by means of a dropping funnel
within 15 minutes. The dropping funnel was rinsed with 20 g of
Solvesso.RTM. 150. After one hour, the reaction had ended.
TABLE-US-00001 Number of Number of Example No. Isocyanate Amount
(g) moles (mmol) Amine amount (g) moles (mmol) 1 IPDI 8.9 40
2-Ethylhexylamine 10.37 80 2 IPDI 8.9 40 n-Dodecylamine 14.87 80 3
IPDI 8.9 40 Ilco-Min 8040 T 21.75 80 4 IPDI 8.9 40 Ilco-Min 8015 C
16.70 80 5 HMDI 10.5 40 Isotridecylamine 16.0 80 6 4,4'-MDI 10.0 40
Isotridecylamine 16.0 80
PREPARATION EXAMPLES 7-12
Polyureas from Diisocyanate, Monoamine and Diamine
[0188] A stirred flask with thermometer and reflux condenser was
initially charged with 160 g of Solvesso.RTM. 150 and the amines,
and the isocyanate was added by means of a dropping funnel within
15 minutes. The dropping funnel was rinsed with 20 g of
Solvesso.RTM. 150. After one hour, the reaction had ended.
TABLE-US-00002 Number of Monoamine Number of Example No. Isocyanate
Amount (g) moles (mmol) Diamine Amount (g) moles (mmol) 7 IPDI 8.9
40 Isotridecylamine 8.0 40 IPDA 3.4 20 8 IPDI 13.3 60
Isotridecylamine 8.0 40 IPDA 6.8 40 9 IPDI 8.9 40 Isotridecylamine
4.0 20 IPDA 5.1 30 10 IPDI 8.9 40 Isotridecylamine 8.0 40 Inipol DS
6.0 20 11 IPDI 6.7 30 Isotridecylamine 4.0 20 Inipol DS 6.0 20 12
IPDI 8.9 40 Isotridecylamine 4.0 20 Inipol DS 9.0 30
PREPARATION EXAMPLES 13 AND 14
Diurethanes from Diisocyanate and Monool
[0189] A stirred flask with thermometer and reflux condenser was
initially charged with 160 g of Solvesso.RTM. 150 and the alcohol,
and the isocyanate was added by means of a dropping funnel within
15 minutes. The dropping funnel was rinsed with 20 g of
Solvesso.RTM. 150. After 24 hours, the reaction had ended.
TABLE-US-00003 Number of Number of Example No. Isocyanate Amount
(g) moles (mmol) Monool Amount (g) moles (mmol) 13 IPDI 8.9 40
Isotridecanol 16.1 80 14 IPDI 8.9 40 n-Tridecanol 16.1 80
PREPARATION EXAMPLES 15-21
Monoureas from Triphosgene and Monoamine
[0190] Preparation example 15: N,N'-Di(2-ethylhexyl)urea:
2-ethylhexylamine (10.0 g, 77.4 mmol) and triethylamine (8.4 g,
83.2 mmol) were dissolved in dichloromethane (125 ml). While
cooling with an ice bath, a solution of triphosgene (4.1 g, 13.8
mmol) in dichloromethane (60 ml) was added dropwise within about 40
min, in the course of which the reaction temperature was kept at
+5.degree. C. to +8.degree. C. Subsequently, the reaction mixture
was stirred at room temperature for 2 h. The reaction mixture was
admixed cautiously with 0.1 M hydrochloric acid (120 ml) and
stirred at room temperature overnight. The phases were separated,
the organic phase was washed with water and dried over MgSO.sub.4,
and the solvent was removed on a rotary evaporator. For
purification, the product was dissolved in acetonitrile (100 ml)
under reflux and then cooled to room temperature, in the course of
which the product separated out as a cloudy oil. The acetonitrile
supernatant was decanted off and the residue was concentrated on a
rotary evaporator. This gave 8.0 g (73%) of the target compound in
the form of a colorless liquid.
[0191] Preparation examples 16-21: Analogous to example 15, the
monoureas of examples 16-21 were obtained from the corresponding
amines by reaction with triphosgene.
TABLE-US-00004 Example Monoamine Monourea obtained 16
2-Propylheptylamine ##STR00005## 17 Tallowamine ##STR00006## 18
Oleylamine ##STR00007## 19 Isotridecylamine (isomer mixture)
##STR00008## 20 Jeffamine .RTM. M-600 (from Huntsman) ##STR00009##
21 Tridecanol*22 BuO, amininated ##STR00010##
USE EXAMPLES 1 TO 3
[0192] Diesel fuel DF1 of the specification specified below was in
each case admixed with 300 ppm by weight of a 60% by weight
solution of a commercial ethylene-vinyl acetate copolymer with a
vinyl acetate content of 30% by weight in Solvent.RTM. Naphtha as a
cold flow improver ("CI") and with 300 ppm by weight of a solution
of two wax antisettling additives ("WASAs") and of a substituted
urea of the general formula (I) in Solvent.RTM. Naphtha ("FI"),
mixed at 40.degree. C. by stirring and then cooled to room
temperature. The CP of these additized fuel samples was determined
to ISO 3015 and the CFPP to EN 116. Thereafter, the additized fuel
samples were cooled to -15.degree. C. in 250 ml glass cylinders in
a cold bath at -25.degree. C. within 3 hours, and stirred at this
temperature for 13 hours. For each sample, the CP was again
determined on the 20% by volume base phase separated off at
-15.degree. C. to ISO 3015, and the CFPP to EN 116.
TABLE-US-00005 Specification of the diesel fuel DF1: Cloud Point
(CP): -7.9.degree. C. Cold Filter Plugging Point (CFPP): -9.degree.
C. Pour Point (PP): -12.degree. C. Density (15.degree. C.): 826.6
kg/m.sup.3 Boiling points: IBP 181.degree. C. 10% 220.degree. C.
20% 234.degree. C. 50% 268.degree. C. 90% 327.degree. C. 95%
341.degree. C. FBP 350.degree. C. WASA additives: K1 =
ethylenediaminetetraacetic acid reacted with 4 mol of hydrogenated
tallowamine K2 = maleic anhydride reacted with 1 mol of
isotridecylamine
[0193] Composition of the FI Solutions:
[0194] FI1: 35 parts by weight of K1 [0195] 10 parts by weight of
K2 [0196] 15 parts by weight of diurea from 1 mol of isophorone
diisocyanate and 2 mol of isotridecylamine [compound of the formula
(11 g)] [0197] 40 parts by weight of Solvent.RTM. Naphtha
[0198] FI2: 35 parts by weight of K1 [0199] 10 parts by weight of
K2 [0200] 15 parts by weight of N,N'-di(2-ethylhexyl)urea
[preparation example 15] [0201] 40 parts by weight of Solvent.RTM.
Naphtha
[0202] FI3: 35 parts by weight of K1 [0203] 10 parts by weight of
K2 [0204] 55 parts by weight of Solvent.RTM. Naphtha
[0205] The following table shows the results of the CP and CFPP
measurements [in each case in .degree. C.], experiment 3 with FI3
serving as a comparison:
TABLE-US-00006 Experiment FI CP CP(up) .DELTA.CP CFPP CFPP(up)
.DELTA.CFPP 1 FI1 -7.6 -6.7 0.9 -27 -26 1 2 FI2 -7.3 -6.8 0.5 -27
-27 0 3 FI3 -7.9 -5.1 2.8 -21 -20 1
[0206] The smaller the deviation (".DELTA.CP") in the CP of the 20%
by volume base phase ["CP(up)"] from the original CP of the
respective fuel sample, the better the dispersion of the paraffins.
The smaller the deviation (".DELTA.CFPP") in the CFPP of the 20% by
volume base phase ["CFPP(up)"] from the original CFPP of the
respective fuel sample, the better the cold flow
characteristics.
* * * * *