Note: Descriptions are shown in the official language in which they were submitted.
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USE OF SUBSTITUTED UREAS OR URETHANES FOR IMPROVEMENT OF THE USE
PROPERTIES OF MINERAL AND SYNTHETIC NONAQUEOUS INDUSTRIAL FLUIDS
Description
The present invention relates to the use of particular substituted ureas or
urethanes for
improvement of the use properties of mineral and synthetic nonaqueous
industrial fluids.
Nonaqueous industrial fluids, which may comprise water components in the
individual case but
whose essential action is based on nonaqueous components, shall be understood
here to mean
lubricants, lubricant compositions and lubricant oils in the widest sense,
especially motor oils,
transmission oils, axle oils, hydraulic fluids, hydraulic oils, compressor
fluids, compressor oils,
circulation oils, turbine oils, transformer oils, gas motor oils, wind turbine
oils, slideway oils,
lubricant greases, cooling lubricants, antiwear oils for chains and conveyor
systems,
metalworking fluids, food-compatible lubricants for industrial processing of
foods, and boiler oils
for industrial cookers, sterilizers and steam peelers. Use properties which
are improved by the
substituted ureas or urethanes are especially lubricity, frictional wear,
lifetime, corrosion
protection, antimicrobial protection, demulsification capacity with regard to
easier removal of
water and impurities, and filterability.
The present invention further relates to the use of the substituted ureas and
urethanes
mentioned in fuels and in lubricant formulations, and to such lubricant
formulations themselves.
The invention further relates to a mixture which comprises the substituted
ureas or urethanes
mentioned and organic compounds which improve the cold flow characteristics of
mineral oils or
crude oils, especially middle distillate fuels, and may already comprise
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. The present
invention further relates to fuels and fuel additive concentrates which
comprise this mixture.
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 ("OF").
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
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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.
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").
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.
By virtue of the additional use of paraffin dispersants or wax antisettling
additives ("WASAs"),
the problems outlined can be reduced.
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
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lower alkyl esters such as methyl esters. These esters are generally also
referred to as
"FAMEs" (fatty acid methyl esters).
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).
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.
There have already been proposals of additives which are intended to improve
the cold
properties of fuels. For instance, US patent 2 657 984, published November 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 F and
was determined in the absence of further additives.
Japanese patent application JP-A S56-93796, published July 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 TH) or trimeric
hexamethylene
diisocyanate (Sumidur0 N75).
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It was an object of the present invention to provide products which bring
about an improvement
of the use properties of mineral and synthetic nonaqueous industrial fluids.
In addition, products which bring about improved cold flow characteristics in
mineral oils and
crude oils were to be provided, especially in middle distillate fuels. More
particularly, the CFPP
for such fuels was to be lowered in a more effective manner.
The object is achieved in accordance with the invention by the use of (i)
substituted ureas or
urethanes of the general formula (I)
R1X-CO-NR3R4 (I)
in which the variable X is R2N or 0 and the variables R, to R4 are each
independently hydrogen,
Ci- to C30-alkyl radicals which may be interrupted by one or more oxygen
atoms, C3- to 030-
alkenyl radicals, Cs- to C30-cycloalkyl radicals, 06- to C30-aryl radicals or
07- to C30-arylalkyl
radicals, where at least one of the variables R1 to R4 must be a radical
having at least 4 carbon
atoms and where one or more of the variables R1 to R4 must be a radical of the
formula (la)
-A-(X'-CO-A')n-X'-CO-NR6R7 (la)
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 NR5
or 0, the variable
n is an integer from 0 to 50 and the variables R5, R6 and R7 are each
independently hydrogen,
Cl- to C30-alkyl radicals which may be interrupted by one or more oxygen
atoms, 03- to 030-
alkenyl radicals, Cs- to C30-cycloalkyl radicals, 06- to C30-aryl radicals or
07- to C30-arylalkyl
radicals, where one or more of the variables R5 to R7 may be a radical having
at least 4 carbon
atoms,
for improvement of the use properties of mineral and synthetic nonaqueous
industrial fluids.
The substituted ureas and urethanes of the general formula (I) are diureas (X
= X' = NR2) or
bisurethanes (X = X' = 0) in the case that they comprise a radical of the
formula (la) where n =
0, and polyureas (X = X' = NR2) or polyurethanes (X = X' = 0) in the case that
they comprise a
radical of the formula (la) where n > 0. The compounds (I) may also comprise a
plurality of, for
example two, three or four, radicals of the formula (la). It is also possible
to use mixed
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urea/urethane compounds (I) with one or more radicals of the formula (la) in
which the individual
variables X and X' may be either NR2 or 0.
Possible C1- to C30-alkyl radicals for R1 to R7 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.
Alkyl radicals interrupted by one or more oxygen atoms for R1 to R7 having up
to 30 carbon
atoms are, for example, radicals of the formula -(CHR8-CH2-0)m-R9 in which the
variable R8 is
hydrogen, a C1- to Ca-alkyl radical such as methyl, ethyl or n-propyl, or
phenyl, the variable R9 is
as defined for the variables R1 to R7, but especially hydrogen or linear or
branched C1- to 020-
alkyl, and the variable m is an integer from 1 to 30. Individual examples of
such radicals are -
(CH2-CH2-0)n,-R9 where m = 1 to 15, -[CH(CH3)-CH2-0]rn-R9 where m = 1 to 25, -
[CH(C2H5)-
CH2-0],õ-R9 where m = 1 to 25 and -(CHPh-CH2-0)m-R9 where m = 1 to 4, where R9
in each
case is hydrogen, methyl, ethyl, 2-ethylhexyl, 2-propylheptyl or isotridecyl.
Possible C3- to C30-alkenyl radicals for R1 to R7 are, for example, linear
alkenyl radicals such as
allyl, oleyl, linolyl and linolenyl.
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.
Possible C5- to C30-cycloalkyl radicals for R1 to R7 are preferably 05- to C10-
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.
Possible C6- to C30-aryl radicals for R1 to R7 are preferably C6- to C10-aryl
radicals, for example
phenyl, naphthyl, tolyl and o-, m- or p-xylyl.
Possible 07- to C30-arylalkyl radicals for R1 to R7 are preferably C7- to C10-
arylalkyl radicals, for
example benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl.
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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.
At least one of the variables R1 to R4 and optionally one or more of the
variables R5 to R7 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 R1 to R7 in that case are generally
short-chain and are, for
example, to Ca-alkyl radicals, or are hydrogen.
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 -(CH2)p- where p = 1 to 20, especially p = 2 to 10, in particular p =
3 to 6; 06- to 010-
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; 06- to Clo-arylene groups such as 1,2-, 1,3- or 1,4-
phenylene; 08- to 014-
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.
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 (la) 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.
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.
In a preferred embodiment, use is made of substituted ureas or urethanes of
the general
formula (I), in which the variable X is R2N where R2 is a radical of the
formula (la) in which the
variable n is 0, the variables R1, R3, R5 and R7 are each hydrogen and the
variables R4 and R6
are each the same Ca- to C30-alkyl radical which may be interrupted by one or
more oxygen
atoms, Ca- to C30-alkenyl radical, 06- to 030-cycloalkyl radical, C6- to C30-
aryl radical or 07- to
C30-arylalkyl radical. The compounds (I) of this embodiment are thus diureas.
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Typical examples of usable diureas and bisurethanes of the general formula (I)
are the
isophorone-derived compounds of the formula (II)
0 R10
N> _______________________________ NI
R11
\R12
0100
R
N N 13
I 15 I
R R14
(II)
with the following variable definitions:
(Ha) R12 = R15 = H, Rlo = R11 = R13 = R14 = n-butyl,
(11b) R11 = R12 = R14 = R15 = H, R13 = R14 = 2-ethylhexyl,
(11c) R11 = R12 = R14 = R15 = H, R13 = R14 = 2_propylheptyl,
(11d) R11 = R12 = R14 = R15 = H, R13 = R14 = n_decyi,
(Ile) R11 = R12 = R14 = R15 = H, R13 = R14 = n-dodecyl,
(11f) R11 = R12 = R14 = R15 = H, R13 = R14 = n-tridecyl,
(11g) R11 = R12 = R14 = R15 = H, R13 = R14 = isotridecyl,
(h1h) R11 = R12 = R14 = R15 = H, R13 = R14 = n-tetradecyl,
(11j) R11 = R12 = R14 = R15 = H, R13 = R14 = n-hexadecyl,
(Ilk) R11 = R12 = R14 = R15 = H, R13 = R14 = n-octadecyl,
(11m) R11 = R12 = R14 = R15 = H, R13 = R14 = oleyl,
(11n) R11 = R12 = R14 = R15 = H, R13 = R14 = phenyl,
and the diureas which are analogous to the compounds (Ha) to (11n) and have
the same R10 to
R15 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 (111)
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0
0
N Ri6
\R17
0
0 R18
N/
0
1 19
R (HI)
with the following variable definitions:
(111a) R17 ..õ.õ R19 .= H, R16 . R18 . n-butyl,
(111b) R17 :: R19 . H, R16 = R18 = 2-ethylhexyl,
(111c) R17 = R19 = H, R16 = R18 = 2-propylheptyl,
(111d) R17 = R19 = H, R16 = R18 = n-decyl,
(111e) R17 = R19 = H, R16 = R18 = n-dodecyl,
(111f) R17 = R19 = H, R16 = R18 = n-tridecyl,
(111g) R17 = R19 = H, R16 = R18 = isotridecyl,
(111h) R17 = R19 = H, R16 = R18 = n-tetradecyl,
(111j) R17 = R19 = H, R16 = R18 = n-hexadecyl,
(111k) R17 = R19 = H, R16 = R18 = n-octadecyl,
(111m) R17 = R19 = H, R16 = R18 = oleyl,
(111n) R17 = R19 = H, R16 = R18 = phenyl,
and the bisurethanes which are analogous to the compounds (111a) to (111n) and
have the same
R16 to R19 radicals and have, as bridging element A, a 1,6-hexamethylene, 2,4-
tolylene, 2,6-
tolylene or diphenylmethan-4,4'-ylene skeleton.
Typical examples of usable polyureas and polyurethanes of the general formula
(1) 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.
The 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 (1) are based on the
reactions of
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isocyanates with appropriate mono- or polyamines and/or appropriate mono- or
polyfunctional
alcohols.
Useful isocyanates include 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.
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-trimethy1-
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.
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 C4-C20-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.
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.
Further useful polyisocyanates include:
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1. lsocyanurate 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.
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.
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.
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.
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.
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11
6. Uretonimine-modified polyisocyanates.
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.
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 (LupranatO MM 103).
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.
The monoamines which can be reacted with the 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,
CA 02865869 2014-08-28
12
diphenylamine, 2,6-xylidine, o-, m- or p-toluidine, a- or 13-naphthylamine, 1-
phenylethylamine
and 2-phenylethylamine. A further example of a usable primary or secondary
monoamine is N-
(3-aminopropyl)imidazole (Lupragen API).
Di- and polyamines which can be reacted with the 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-aminomethy1-3,5,5-
trimethylcyclohexane
(isophoronediamine), 4,4'-diaminodicyclohexylmethane, 3,3'-dimethy1-
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-
aminopropy1)-methylamine.
Examples of alcohols which can be reacted with the 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, leyl 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-ethyny1-1-cyclohexanol, 2-mercaptoethanol, 2-methyl-3-butyn-2-ol, 3-
butyn-2-ol, 4-ethy1-1-
octyn-3-ol, ethylenechlorohydrin, propargyl alcohol,
dimethylaminoethoxyethanol (Lupragen
CA 02865869 2014-08-28
13
N107), dimethylethanolamine (Lupragen N101) and
trimethylaminoethylethanolamine
(Lupragen 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.
Further examples of alcohols which can be reacted with the 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.
Examples of low molecular weight diols of this kind are ethylene glycol,
propane-1,2-diol,
propane-13-diol, butane-1,3-diol, butane-2,3-diol, but-2-ene-1,4-diol, but-2-
yne-1,4-diol,
pentane-12-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-dimethy1-2,5-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-(CH2)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-18-diol,
decane-1,10-diol and
dodecane-1,12-diol.
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
pentanedio1-1,5 and neopentyl glycol.
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.
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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.
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-(CH2)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.
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.
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-(CH2)z-COOH in
which z is a
number from 1 to 20, especially an odd number from 3 to 19, for example c-
caprolactone, 13-
propiolactone, y-butyrolactone and/or methyl-g-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 c-
caprolactone
CA 02865869 2014-08-28
are of particular interest. It is also possible to use lower molecular weight
polyester diols or
polyether dials 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.
In addition, useful higher molecular weight dials are also polyether dials.
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 BF3, 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.
The polyester dials and polyether dials mentioned can also be used as mixtures
in a ratio of
0.1:1 to 1:9.
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 C,
especially of 50 to
150 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.
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(11) 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-
tetramethy1-3,5-
CA 02865869 2014-08-28
16
heptanedionate. In addition, it is also possible to use bismuth and cobalt
catalysts and cesium
salts as catalysts, for example cesium carboxylates.
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.
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.
The substituted ureas and urethanes described are likewise suitable for
improvement of the cold
flow properties and/or the lubricant properties and/or the conductivity and/or
the oxidation
insensitivity and/or the dispersion characteristics of mineral oils and crude
oils. The
corresponding uses therefore also form part of the subject matter of the
present invention.
The substituted ureas and urethanes described are preferably suitable for
improvement of the
cold flow properties and/or of the lubricant properties of fuels, especially
of middle distillate
fuels. In this context, the substituted ureas and urethanes described are
particularly used for
dispersion or for promoting dispersion of paraffin crystals which have
precipitated out of fuels
under cold conditions.
In a particularly preferred embodiment, the substituted ureas and urethanes
described are used
in the dispersion or for promoting dispersion of paraffin crystals which
precipitate out of fuels
under cold conditions, in combination with at least one organic compound which
improves the
cold flow characteristics of middle distillate fuels and is selected from
(al) copolymers of a 02- to C40-olefin with at least one further ethylenically
unsaturated
monomer;
(a2) comb polymers;
(a3) polyoxyalkylenes;
(a4) polar nitrogen compounds;
CA 02865869 2014-08-28
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(a5) sulfocarboxylic acids or sulfonic acids or derivatives thereof; and
(a6) poly(meth)acrylic esters.
It is possible to use either mixtures of different representatives from one of
the particular classes
(al) to (a6) or mixtures of representatives from different classes (al) to
(a6).
Preferably, substituted ureas or urethanes of the general formula (I) are used
in mineral oils or
crude oils which comprise, as a further component, at least one (al) copolymer
of a C2- to C40-
olefin with at least one further ethylenically unsaturated monomer.
Suitable 02- to C40-olefin monomers for the copolymers (al) 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 (a-olefins) or internally.
However, preference is
given to a-olefins, more preferably a-olefins having 2 to 6 carbon atoms, for
example propene,
1-butene, 1-pentene, 1-hexene and in particular ethylene.
In the copolymers (al), 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 C2- to 040-olefin base monomer. When, for example, the olefin
base monomer
used is ethylene or propene, suitable further olefins are especially Clo- to
C40-a-olefins. Further
olefins are in most cases only additionally copolymerized when monomers with
carboxylic ester
functions are also used.
Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid
with Cr to C20-
alkanols, especially C1- to 010-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.
Suitable alkenyl carboxylates are, for example, 02- to 014-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 a-position to the carboxyl group, the a-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.
CA 02865869 2014-08-28
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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
(al) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs"). Very
particular
preference is given to using, as component (al), at least one such ethylene-
vinyl acetate
copolymer. Ethylene-vinyl acetate copolymers usable particularly
advantageously and their
preparation are described in WO 99/29748.
Suitable copolymers (al) 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.
In a further preferred embodiment, (al) is at least one terpolymer of a C2- to
C40-a-olefin, a Cl-
to C20-alkyl ester of an ethylenically unsaturated monocarboxylic acid having
3 to 15 carbon
atoms and a 02- to 014-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.
The or the further ethylenically unsaturated monomer(s) are copolymerized into
the copolymers
(al) 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 (al) therefore originates
generally from the 02 to
040 base olefins.
The copolymers (al) preferably have a number-average molecular weight M5 of
1000 to 20 000
daltons, more preferably 1000 to 10 000 daltons and especially 1000 to 8000
daltons.
As well as the preferred copolymers of class (al), it is also advantageously
possible to use the
compounds of classes (a2) to (a6) as components together with the substituted
ureas and
urethanes described.
Comb polymers suitable as compounds (a2) 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
CA 02865869 2014-08-28
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polymers (a2) are, for example, those obtainable by the copolymerization of
maleic anhydride or
fumaric acid with another ethylenically unsaturated monomer, for example with
an a-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 a-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.
Polyoxyalkylenes suitable as compounds (a3) 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
US 4,491,455.
Suitable compounds (a4) are the polar nitrogen compounds described below under
component
(ii).
Suitable compounds (a5) 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.
Poly(meth)acrylic esters suitable as compounds (a6) 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. The copolymer
optionally 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
C14 and C15
alcohols, the acid groups having been neutralized with hydrogenated tallamine.
Suitable
poly(meth)acrylic esters are described, for example, in WO 00/44857.
CA 02865869 2014-08-28
The substituted ureas and urethanes described are additionally suitable for
improvement of the
cold flow properties and/or of the lubrication properties of mineral and
synthetic lubricants and
lubricant formulations produced therefrom. The corresponding uses therefore
also form part of
the subject matter of the present invention. The present invention likewise
provides these
lubricant formulations which have been produced from mineral and synthetic
lubricants and
which comprise at least one of the substituted ureas described or at least one
of the substituted
urethanes described and at least one further additive component customary for
lubricant
formulations.
Lubricant formulations shall be understood here to mean especially motor oils,
and transmission
oils including manual and automatic oils. Motor oils consist typically of
mineral base oils which
comprise predominantly paraffinic constituents and are produced by complex
workup and
purification operations in the refinery, with a proportion of normally about 2
to 10% by weight of
additives (based on the active substance contents). For specific applications,
for example high-
temperature uses, the mineral base oils can be replaced partly or fully by
synthetic components
such as organic esters, synthetic hydrocarbons such as olefin oligomers, poly-
a-olefins or
polyolefins, or hydrocracking oils. Motor oils must also have sufficiently
high viscosities at high
temperatures to ensure an impeccable lubrication effect and good sealing
between cylinder and
piston. In addition, the flow properties of motor oils must also be such that
the engine can be
started without any problem at low temperatures. Motor oils must be oxidation-
stable and, even
under severe working conditions, must generate only a low level of
decomposition products in
liquid or solid form and deposits. Motor oils disperse solids (dispersant
characteristics), prevent
deposits (detergent characteristics), neutralize acidic reaction products and
form an antiwear
film on the metal surfaces in the engine. Motor oils for internal combustion
engines, especially
for gasoline engines, Wankel engines, two-stroke engines and diesel engines,
are typically
characterized by viscosity classes (SAE classes); of particular interest here
are fuel-economy
motor oils, especially of the SAE 5 W to 20 W viscosity classes to DIN 51511.
Transmission oils including manual and automatic oils are of similar
composition to motor oils in
terms of their base components and additives. A high proportion of the force
is transmitted in
the gear system of gearboxes through the liquid pressure in the transmission
oil between the
teeth. The transmission oil must accordingly be such that it withstands
sustained high pressures
without decomposing. As well as the viscosity properties, the crucial
parameters here are wear,
pressure resistance, friction, shear stability, traction and run-in
characteristics.
The inventive lubricant formulations comprise the substituted ureas or
urethanes described in
an amount of typically 0.001 to 20% by weight, preferably 0.01 to 10% by
weight, especially
CA 02865869 2014-08-28
21
0.05 to 8% by weight and in particular 0.1 to 5% by weight, based on the total
amount of the
lubricant formulation.
The inventive lubricant formulations may be additized in a customary manner,
which means that
they comprise, as well as the base oil components typical for the end use
thereof, such as
mineral or synthetic hydrocarbons, polyethers or esters or mixtures thereof,
also customary
additives other than dispersants, such as detergent additives (HD additives),
antioxidants,
viscosity index improvers, pour point depressants (cold flow improvers),
extreme pressure
additives, friction modifiers, antifoam additives (defoamers), corrosion
inhibitors (metal
deactivators), emulsifiers, dyes and fluorescent additives, preservatives
and/or odor improvers,
in the amounts customary therefor. It will be appreciated that the substituted
ureas and
urethanes described can also be used in the lubricant formulations together
with other additives
with dispersing action, more particularly with other ashless additives with
dispersing action, for
example with polyisobutylsuccinic acid derivatives.
The present invention also provides a mixture comprising
(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)
(ii) 0 to 50% by weight, especially 0 to 40% by weight and in particular 0
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
(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, where the sum of all
components (i) to
(iii) adds up to 100% by weight.
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.
CA 02865869 2014-08-28
22
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.
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.
The inventive mixture is thus 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 C.
The inventive interaction of components (i), (iii) and optionally (ii) 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.
Component (ii) ensures dispersion 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 this case, component (ii) enhances the possible dispersing action
of component (i),
the substituted ureas or urethanes.
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).
CA 02865869 2014-08-28
23
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 >NR23 in which R23 is a C8-C40-
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 Cs-am-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.
Further examples of suitable polar nitrogen compounds are ring systems which
bear at least two
substituents of the formula -A"-NR24R25 in which A" is a linear or branched
aliphatic hydrocarbyl
group optionally interrupted by one or more moieties selected from 0, S, NR36
and CO, and R24
and R25 are each a C9- to 040-hydrocarbyl radical optionally interrupted by
one or more moieties
selected from 0, S, NR36 and CO and/or substituted by one or more substituents
selected from
OH, SH and NR36R37, where R36 is Ci- to C40-alkyl optionally interrupted by
one or more
moieties selected from CO, NR37, 0 and S and/or substituted by one or more
radicals selected
from NR38R39, 0R39, SR38, C0R38, C00R39, C0NR38R39, aryl and heterocyclyl,
where R38 and
R39 are each independently selected from H and Ci- to C4-alkyl and where R37
is H or R36.
More particularly, component (ii) is an oil-soluble reaction product of
poly(02- to C20-carboxylic
acids) having at least one tertiary amino group with primary or secondary
amines. The poly(C2-
to Carcarboxylic 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
CA 02865869 2014-08-28
24
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.
Component (ii) is preferably an oil-soluble reaction product based on poly(C2-
to C20-carboxylic
acids) which have at least one tertiary amino group and are of the general
formula IVa or IVb
HOOC, ,COOH
HOOCõN, ,N, ,COOH
A B (IVa)
-B. .B.
HOOC N COON
B. COON (IVb)
in which the variable A* is a straight-chain or branched C2- to C6-alkylene
group or the moiety of
the formula V
HOOC 13, CH2-C H2-
-
CH2-C H2-
(V)
and the variable B is a C1- to C19-alkylene group.
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.
Straight-chain or branched C2- to C6-alkylene groups of the variable A* are,
for example, M-
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-dimethy1-1,3-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.
C1- to Cis-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,
CA 02865869 2014-08-28
nonadecamethylene and especially methylene. The variable B comprises
preferably 1 to 10 and
especially 1 to 4 carbon atoms.
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.
These amines underlying the oil-soluble reaction products of component (ii)
are preferably
secondary amines and have the general formula HN(R*)2 in which the two
variables R* are each
independently straight-chain or branched Clo- to C3o-alkyl radicals,
especially 014- to C24-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.
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.
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.
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.
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
CA 02865869 2014-08-28
26
thereof, with primary or secondary amines having straight-chain or branched
010 to C3o 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.
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.
=
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(02- to C2o-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.
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.
More particularly, component (iii), which generally represents a different
substance class than
component (ii), is selected from the abovementioned substance classes (al) to
(a6), (al) being
of particular interest.
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
CA 02865869 2014-08-28
27
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.
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.
The inventive mixture can be used as an additive to middle distillate fuels
which consist
(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
(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.
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 Ci- to Ca-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").
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.
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
CA 02865869 2014-08-28
28
biodiesel. Vegetable fats can in principle likewise be used as a source for
biodiesel, but play a
minor role.
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.
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.
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").
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.
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 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.
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 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
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 C, especially
below 360 C and in special cases below 330 C.
CA 02865869 2014-08-28
29
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.
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.
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.
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 Al2, p. 617 if., which is hereby incorporated explicitly by reference).
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 (iii)
and optionally (ii) -
typically to the standard EN 116, and the OP 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
CA 02865869 2014-08-28
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.
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.
The present invention also provides middle distillate fuels, optionally with a
content of biofuel
oils (biodiesel).
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.
The examples which follow are intended to illustrate the present invention
without restricting it.
CA 02865869 2014-08-28
31
Abbreviations:
Ilco-Min 8015 C C12-C14 cocoamine technical grade, equivalent weight 208
Ilco-Min 8040 T C16-C18 tallowamine, partly unsaturated, equivalent weight
271
lnipol DS N-tallowalky1-1,3-propanediamine, equivalent weight 299
IPDA isophoronediamine
IPDI isophorone diisocyanate
HMDI dicyclohexylmethane 4,4'-diisocyanate
=
4,4'-MDI diphenylmethane 4,4'-diisocyanate
Solvesso 150 aromatic solvent, boiling range 181-207 C
Preparation examples 1-6: Diureas from diisocyanate and monoamine
A stirred flask with thermometer and reflux condenser was initially charged
with 160 g of
Solvesso 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 150.
After one hour,
the reaction had ended.
Example lsocyanate Amount (g) Number of Amine amount (g) Number of
No. moles moles
(mmol) (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 8040T 21.75 80
4 IPDI 8.9 40 Ilco-Min 8015 C 16.70 80
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
A stirred flask with thermometer and reflux condenser was initially charged
with 160 g of
Solvesso 150 and the amines, and the isocyanate was added by means of a
dropping funnel
CA 02865869 2014-08-28
32
within 15 minutes. The dropping funnel was rinsed with 20 g of Solvesso0 150.
After one hour,
the reaction had ended.
Example Isocyanate Amount (g) Number of Monoamine Amount (g) Number of
No. moles moles
(mmol) Diamine (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
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
A stirred flask with thermometer and reflux condenser was initially charged
with 160 g of
Solvesso0 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 Solvesso0 150.
After 24 hours,
the reaction had ended.
Example lsocyanate Amount (g) Number of Monool Amount (g) Number of
No. moles moles
(mmol) (mmol)
13 IPDI 8.9 40 Isotridecanol 16.1 80
14 IPDI 8.9 40 16.1 80
n-Tridecanol
Use examples 1 to 3:
Diesel fuel DF1 of the specification specified below was 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 Naphtha as a cold flow improver ("Cl")
and with 300 ppm
CA 02865869 2014-08-28
33
by weight of a solution of two wax antisettling additives ("WASAs") and of a
substituted urea of
the general formula (1) in Solvent Naphtha ("Fr), mixed at 40 C by stirring
and then cooled to
room temperature. The OP of this additized fuel sample was determined to ISO
3015 and the
CFPP to EN 116. Thereafter, the additized fuel sample was cooled to -15 C in a
250 ml glass
cylinder in a cold bath at -25 C within 3 hours, and stirred at this
temperature for 13 hours. For
each sample, the OP was again determined on the 20% by volume base phase
separated off at
-15 C to ISO 3015, and the CFPP to EN 116.
Specification of the diesel fuel DF1:
Cloud Point (CP): -7.9 C
Cold Filter Plugging Point (CFPP): -9 C
Pour Point (PP): -12 C
Density (15 C): 826.6 kg/m3
Boiling points: IBP 181 C
10% 220 C
20% 234 C
50% 268 C
90% 327 C
95% 341 C
FBP 350 C
= WASA additives: K1 = ethylenediaminetetraacetic
acid reacted with 4 mol of
hydrogenated tallowamine
K2 = maleic anhydride reacted with 1 mol of isotridecylamine
Composition of the Fl solutions:
F11: 35 parts by weight of K1
parts by weight of K2
parts by weight of diurea from 1 mol of isophorone diisocyanate and 2 mol of
isotridecylamine [compound of the formula (11g)]
40 parts by weight of Solvent Naphtha
F12: 35 parts by weight of K1
10 parts by weight of K2
55 parts by weight of Solvent Naphtha
CA 02865869 2014-08-28
34
The following table shows the results of the CF and CFPP measurements [in each
case in C],
experiment 2 with FI2 serving as a comparison:
ExperimentFI CP CP(up) ACP CFPP CFPP(up) ACFPP
1 FI1 -7.6 -6.7 0.9 -27 -26 1
3 FI3 -7.9 -5.1 2.8 -21 -20 1
The smaller the deviation ("ACP") in the CF of the 20% by volume base phase
["CP(up)"] from
the original OP of the respective fuel sample, the better the dispersion of
the paraffins. The
smaller the deviation ("ACFPP") 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.
