Note: Descriptions are shown in the official language in which they were submitted.
:A 02819770 2013-08-03
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Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines
and use thereof as a fuel additive or lubricant additive
Description
The present invention relates to novel polytetrahydrobenzoxazines which can be
defined by the preparation process specified below or alternatively by the
general
structural formula I specified below. The polytetrahydrobenzoxazines may also
be
present in quaternized form.
The present invention further relates to novel bistetrahydrobenzoxazines which
occur as intermediates in the preparation of the polytetrahydrobenzoxazines.
The present invention further relates to the use of the
polytetrahydrobenzoxazines
and of the bistetrahydrobenzoxazines as a fuel additive or lubricant additive,
especially as a detergent additive for diesel fuels, in particular for direct-
injection
diesel engines, and to additive concentrates, fuel compositions and lubricant
compositions which comprise the polytetrahydrobenzoxazines or
bistetrahydrobenzoxazines.
In direct-injection diesel engines, the fuel is injected and distributed
ultrafinely
(nebulized) by a multihole injection nozzle which reaches directly into the
combustion chamber in the engine, instead of being introduced into a
prechamber
or swirl chamber as in the case of the conventional (chamber) diesel engine.
The
advantage of the direct-injection diesel engines lies in their high
performance for
diesel engines and a nevertheless low fuel consumption. Moreover, these
engines
achieve a very high torque even at low speeds.
At present, essentially three methods are being used to inject the fuel
directly into
the combustion chamber of the diesel engine: the conventional distributor
injection
pump, the pump-nozzle system (unit-injector system or unit-pump system) and
the
common-rail system.
In the common-rail system, the diesel fuel is conveyed by a pump with
pressures up
to 2000 bar into a high-pressure line, the common rail. Proceeding from the
common rail, branch lines run to the different injectors which inject the fuel
directly
into the combustion chamber. The full pressure is always applied to the common
rail, which enables multiple injection or a specific injection form. In the
other
injection systems, in contrast, only lesser variation of injection is
possible. The
injection in the common rail is divided essentially into three groups: (1.)
pre-
injection, by which essentially softer combustion is achieved, such that hard
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2
combustion noises ("nailing") are reduced and the engine appears to run
quietly;
(2.) main injection, which is responsible especially for a good torque
profile; and (3.)
post-injection, which especially ensures a low nitrogen oxide value in the
exhaust
gas. In this post-injection, the fuel is generally not combusted, but instead
evaporated by residual heat in the cylinder. The exhaust gas/fuel mixture
formed is
transported to the exhaust gas system, where the fuel, in the presence of
suitable
catalysts, acts as a reducing agent for the nitrogen oxides.
The variable, cylinder-individual injection in the common-rail injection
system can
positively influence the pollutant emission of the engine, for example the
emission
of nitrogen oxides (NO), carbon monoxide (CO) and especially of particulates
(soot). This makes it possible, for example, that engines equipped with common-
rail
injection systems can meet the Euro 4 standard theoretically even without
additional particulate filters.
In modern common-rail diesel engines, under particular conditions, for example
when biodiesel-containing fuels or fuels with metal impurities such as zinc
compounds, copper compounds, lead compounds and further metal compounds
are used, deposits can form on the injector orifices, which adversely affect
the
injection performance of the fuel and hence impair the performance of the
engine,
i.e. especially reduce the power, but in some cases also worsen the
combustion.
The formation of deposits is enhanced further by further developments of the
injector construction, especially by the change in the geometry of the nozzles
(narrower, conical orifices with rounded outlet). For lasting optimal
functioning of
engine and injectors, such deposits in the nozzle orifices must be prevented
or
reduced by suitable fuel additives.
WO 2009/040582 describes the use of a Mannich reaction product of an aldehyde,
a polyamine and a substituted phenol with a substituent which has a mean
molecular weight of less than 300 as a diesel additive for improving the
efficiency of
the diesel engine, especially reducing the power loss in the engine and
reducing the
level of deposits on the injectors.
WO 2009/040583 describes the use of the combination of a Mannich reaction
product of an aldehyde, a polyamine and a substituted phenol with a
polyisobutylsuccinimide as a diesel additive for improving the efficiency of
the diesel
engine, especially reducing the power loss in the engine and reducing the
level of
deposits on the injectors.
WO 2009/040584 describes a metal-containing diesel fuel which, as an
efficiency-
improving additive, comprises a Mannich reaction product of an aldehyde, a
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polyamine of the structure of an optionally substituted ethylenediamine and a
substituted phenol. The improvement in efficiency consists especially in the
reduction in the power loss in the engine, the reduction in the level of
deposits on
the injectors, the reduction in the level of deposits in the fuel filter, and
the reduction
of fuel consumption.
WO 2009/040585 describes the use of a Mannich reaction product of an aldehyde,
a polyamine and a substituted phenol, where the molar ratio of phenol to
polyamine
in the reaction mixture is at least 1.5 : 1, as a diesel additive for
improving the
efficiency of the diesel engine, especially reducing the power loss in the
engine,
reducing the level of deposits on the injectors, reducing the level of
deposits in the
fuel filter and reducing fuel consumption.
GB-A 2 468 130 discloses a diesel fuel which comprises one or more efficiency-
enhancing additives from the group of the polymeric or nonpolymeric phenol-
ammonia-aldehyde Mannich adducts, the polyisobutylsuccinimides, the
antioxidants, the mixtures of polyisobutylsuccinimides with polyether carrier
oils and
the phenol-polyamine-aldehyde Mannich adducts. These additives bring about an
improvement in the efficiency of the diesel engine and a reduction in the
level of
deposits in the diesel engine.
WO 2008/027881 describes quaternary ammonium salts as reaction products of
Mannich adducts which have a tertiary amino group and are obtainable from a
substituted phenol, an aldehyde and an amine, and a quaternizing agent. These
quaternary ammonium salts are suitable inter alia as additives in fuels.
However, the additive systems described in the prior art have a series of
disadvantages ¨ especially in the case of direct-injection diesel engines, in
particular in those with common-rail injection systems. Excessive deposits
still
occur in the injection systems of the engines, and the fuel consumption and
the
power loss are still too high. Furthermore, the diesel fuels additized with
the additive
systems described in the prior art still have low-temperature properties which
are in
need of improvement. The compatibility of motor oils with the additive systems
described in the prior art is also still not optimal.
It is therefore an object of the present invention to provide fuel and
lubricant
additives with improved efficiency. The object is achieved by the
polytetrahydrobenzoxazines and bistetrahydrobenzoxazines described
hereinafter.
The inventive polytetrahydrobenzoxazines can be defined by the process for
preparing them. Accordingly, the present invention provides
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polytetrahydrobenzoxazines which are obtainable by the reaction steps of
(A) reacting at least one diamine of the general formula H2N-A-NH2, in
which the
bridging member A is Cl- to C20-alkylene which may be interrupted by up to
10 oxygen atoms and/or tertiary nitrogen atoms, 02- to C20-alkenylene, 05- to
C2o-cycloalkylene, 06- to C20-arylene or 07- to C20-aralkylene with at least
one
Cl- to C12-aldehyde and at least one Cl- to C8-alkanol at a temperature of 20
to 80 C with elimination and removal of water, where both the aldehyde and
the alcohol may be used in each case in more than double the molar amount
compared to the diamine;
(B) reacting the condensation product from reaction step (A) with at least
one
phenol which bears at least one long-chain substituent having 6 to 30 carbon
atoms in a stoichiometric ratio to the diamine originally used in step (A) of
1.2
:1 to 3.5 : 1 at a temperature of 30 to 120 C;
(C) heating the reaction product from reaction step (B) to a temperature of
125 to
280 C for at least 10 minutes.
Cl- to 020-alkylene for the bridging member A represents linear or mono- or
polybranched saturated hydrocarbon bridging members having 1 to 20, especially
1
to 10 and in particular 1 to 4 carbon atoms, for example -CH2-, -(CH2)2-, -
CH(0H3)-,
-(CH2)3-, -CH2-CH(CH3)-, -(CH2)4-, -0H20H2-CH(CH3)-, -0H2-CH(CH3)-CH2-, -
(CH2)5-, -CH2-C(CH3)2-CH2-, -(CH2)6-, -CH(CH3)-(CH2)2-CH(CH3)-, -CH(CH3)-
(0H2)3-CH(CH3)-, -(CH2)7- or -(CH2)8-.
In the case of an interruption of the C1- to 020-alkylene bridging member by
up to
10, especially by up to 4 and in particular by one or two or three oxygen
atoms
and/or tertiary nitrogen atoms, the following are examples of possible
structures for
A: -0H2-0-CH2-, -CH2CH2-0-CH2CH2-, -CH2-0-CH2CH2-0-CH2-, -CH2-0-CH2CH2-
0-CH2CH2-0-CH2-, -CH2CH2-0-CH2CH2-0-CH2CH2-, -CH2CH2-0-0H20H2-0-
CH2CH2-0-CH2CH2-, CH2-N(CH3)-CH2- or -CH2CH2-N(CH3)-0H20H2-. The side
chains on interrupting tertiary nitrogen atoms are typically Cl- to Ca-alkyl
radicals
such as methyl or ethyl; in the case of occurrence of such tertiary nitrogen
atoms,
the maximum carbon number of 20, especially of 10 and in particular of 4 is
not
exceeded even including the alkyl side chains.
02- to Caralkenylene for the bridging member A represents mono- or
polyunsaturated, especially mono unsaturated, hydrocarbon bridging members
having 1 to 20, especially 1 to 10 and in particular 1 to 4 carbon atoms, for
example
1
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A :A 02819770 2013-08-03
-CH=CH-, -CH=CH-CH2-, -CH=CH-CH2-CH2-, -CH2-CH=CH-CH2-, -CH=CH-
CH=CH-, -CH(CH3)-CH=CH- or
-CH2-C(CH3)=CH-.
5 Ca- to C20-cycloalkylene, especially 05- to Ca-cycloalkylene, for the
bridging member
A is, for example, 1,1-, 1,2- or 1,3-cyclopentylene, 1,1-, 1,2-, 1,3- or 1,4-
cyclohexylene, 1,1-, 1,2-, 1,3- or 1,4-cycloheptylene or 1,1-, 1,2-, 1,3-, 1,4-
or 1,5-
cyclooctylene, which may additionally bear one or more Cl- to C4-alkyl
substituents
such as methyl or ethyl groups, or is a dicyclohexylmethane skeleton with free
valences in the 4 and 4' positions on the cyclohexyl rings.
06- to 020-arylene, especially 06- to C14-arylene, for the bridging member A
is, for
example, ortho-, meta- or para-phenylene, naphthylenes, anthracylenes, phenan-
thrylenes or 4,4'-diphenylene, which may additionally bear one or more Cl- to
04-
alkyl substituents such as methyl or ethyl groups on their aromatic rings.
07- to 020-aralkylene, especially 07- to C12-aralkylene, for the bridging
member A
represents structures with one free valence originating from an sp2-hybridized
carbon atom in an aromatic ring and with the other free valence originating
from an
sp3-hybridized carbon atom in a size chain of the aromatic ring such as a
phenyl
ring, or with both free valences originating from sp3-hybridized carbon atoms
in
different side chains of an aromatic ring, for example ortho-, meta- or para-
C6F14-
CH2-, ortho-, meta- or para-C6H4-CH2CH2-, ortho-, meta- or para-06H4-(CH2)3-,
ortho-, meta- or para-C6H4-(CH2)4- or ortho-, meta- or para-CH2-C6H4-CH2-=
In a preferred embodiment, the inventive polytetrahydrobenzoxazines are
obtainable in reaction step (A) from at least one diamine of the general
formula
H2N-(CH2).-NH2 [i.e. A = -(CH2),-], in which xis a number from Ito 10.
Particular
preference is given to diamines of the general formula H2N-(CH2)x-NH2, in
which x
is a number from 1 to 8, especially a number from 1 to 4, in particular the
number 2.
When x = 2, said diamine is 1,2-ethylenediamine.
Suitable Ci- to 012-aldehydes, especially 01- to 07-aldehydes, are, for
example,
formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde or
benzaldehyde. In a preferred embodiment, the inventive
polytetrahydrobenzoxazines are obtainable in reaction step (A) from
formaldehyde
or a polymeric form of formaldehyde, such as paraformaldehyde or 1,3,5-
trioxane.
Suitable Ci- to Ca-alkanols, especially Cl- to 04-alkanols, are, for example,
methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,
isobutanol, tert-
butanol, n-pentanol, sec-pentanol, isopentanol, tert-pentanol, n-hexanol, n-
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heptanol, n-octanol, 2-ethylhexanol, n-nonanol, isononanol or n-decanol, and
also
mixtures of such alkanols. In a preferred embodiment, the inventive
polytetrahydrobenzoxazines are obtainable in reaction step (A) from at least
one
C3- or C4-alkanol.
The diamine of the formula H2N-A-NH2 is reacted with the Ci- to Cu-aldehyde
and
the Cl- to C8-alkanol generally at room temperature to slightly elevated
temperature, i.e. at 20 to 80 C, especially at 25 to 70 C and in particular at
30 to
60 C. Preference is given to working under gentle vacuum, i.e. at 20 mbar to
standard pressure, especially at 30 to 700 mbar, in particular at 40 to 500
mbar, in
order to be able to better remove the water eliminated from the reaction
mixture ¨
for example by azeotropic distillation. The optimal temperature and pressure
settings depend of course on the boiling point of the Cl- to C8-alkanol(s)
used. The
preferred ranges specified above for temperature and pressure settings are
particularly recommended in the case of use of C3- or C4-alkanols.
The diamine of the formula H2N-A-NH2 is reacted with the C1- to Cu-aldehyde
and
the Ci- to C8-alkanol advantageously in an inert organic solvent or a mixture
of such
solvents, especially a hydrocarbon such as hexane, cyclohexane, toluene or
xylene, or a halohydrocarbon such as chloroform or chlorobenzene. In many
cases,
it has been found to be advantageous first to initially charge the Ci- to Cu-
aldehyde
and the Cl- to C8-alkanol at room temperature or very low temperature in the
inert
solvent, then to add the diamine and then ¨ optionally under reduced pressure
¨ to
heat to reaction temperature and to remove the water eliminated. The reaction
time
is typically 1 to 10 hours.
In a preferred embodiment, the stoichiometric ratio of diamine to aldehyde in
reaction step (A) is 1 : 4, where a deviation from this ratio of up to 10% can
be
tolerated, and the alkanol is used in at least 3.5 times the molar amount,
especially
4 times the molar amount, compared to the diamine. The alcohol can also be
used
in a higher amount, i.e. in excess, for example in 4 to 8 times the molar
amount
compared to the diamine. The preferred stoichiometric ratio of diamine to
aldehyde
is thus typically in the range of 1 : (3.6 ¨ 4.4) or of (0.9¨ 1.1) : 4,
especially of
1 : (3.9 ¨ 4.1) or of (0.97-1.03) :4.
In reaction step (A), the active agent for the reaction with the phenol is
obtained in
reaction step (B), which is generally a mixture of the partly or fully
hydroxyalkylated
diamine which is in partly or fully etherified form with the Ci- to C8-
alkanol, and
possibly ring-closed conversion products such as imidazolidines. The
individual
components of this mixture are typically in chemical equilibrium with one
another,
such that normally all or almost all components of this mixture are available
for
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:A 02819770 2013 06 03
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further reaction in the next reaction step, (B), for the purposes of the
present
invention.
Such a mixture, which is obtainable, for example, by reacting ethylenediamine,
formaldehyde and isobutanol, is represented below by way of example with its
components:
OH
o 4 N OH
H2N + H H HON
HO)
OH
11 4
OH OH
HO)
HO)
0 N
o
HO
HON__N
The phenol used in reaction step (B) bears, as the at least one long-chain
substituent having 6 to 3000 carbon atoms, typically a corresponding
hydrocarbyl
radical. A hydrocarbyl radical shall be understood here to mean a hydrocarbon
:A 02819770 2013-08-03
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8
radical of any structure which, however, in a minor amount, may also comprise
heteroatoms such as oxygen atoms and/or nitrogen atoms and/or halogen atoms,
and/or may bear functional groups such as hydroxyl groups, carboxyl groups,
carboxylic ester groups, cyano groups, nitro groups and/or sulfo groups. Said
long-
chain hydrocarbyl radical may be saturated or unsaturated in nature; it may
have a
linear or branched structure; it may comprise aromatic and/or heterocyclic
substructures. The at least one long-chain substituent on the phenol serves
principally to make the inventive polytetrahydrobenzoxazines better soluble in
mineral oil products such as fuels and lubricants.
This relatively long-chain hydrocarbyl radical on the phenol is preferably a
hydrocarbyl radical having 6 to 30 carbon atoms or a polyisobutyl radical
having 16
to 3000 carbon atoms.
Useful hydrocarbyl radicals having 6 to 30 carbon atoms on the phenol are
preferably 06- to 030-alkenyl radicals, especially C7- to C20-alkenyl
radicals, in
particular C8- to 018-alkenyl radicals and very especially 06- to C30-alkyl
radicals,
especially 07- to C18-alkyl radicals, and in particular 08- to C12-alkyl
radicals. The
phenol may bear one, two or three such long-chain substituents; the phenol
preferably bears one such long-chain substituent. In addition to the long-
chain
substituents, the phenol may also bear one, two or three shorter-chain alkyl
or
alkenyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-
butyl,
isobutyl, tert-butyl, vinyl or allyl radicals, and/or one, two or three
functional groups
such as halogen atoms, for example chlorine or bromine, nitro groups, cyano
groups, carboxyl groups, carboxylic ester groups or sulfo groups, where the
total
number of substituents on the phenol is not more than 5, preferably not more
than 4
and in particular not more than 3.
Examples of said phenols having at least one long-chain substituent having 6
to 30
carbon atoms are phenols with an n-hexyl, n-heptyl, n-octyl, tert-octyl, 2-
ethylhexyl,
n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl,
isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, oleyl, linolyl or
linolenyl radical in
the ortho or para position, and also ortho-cresol having one of the
abovementioned
long-chain alkyl or alkenyl radicals in the 4 or 6 position, meta-cresol
having one of
the abovementioned long-chain alkyl or alkenyl radicals in the 4 or 6
position, para-
cresol having one of the abovementioned long-chain alkyl or alkenyl radicals
in the
2 or 6 position, and phenols having two identical or different abovementioned
long-
chain alkyl or alkenyl radicals in the 2 and 4 position.
In the case of polyisobutyl radicals, these comprise preferably 21 to 1000,
especially 26 to 3000 or especially 26 to 500, in particular 30 to 3000 or in
particular
:A 02819770 2013-08-03
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30 to 250 carbon atoms, or they have number-average molecular weights Mn of
183
to 42 000, preferably 500 to 15 000, especially 700 to 7000, in particular 900
to
3000, most preferably 900 to 1100.
The phenol may bear one, two or three such polyisobutyl radicals; the phenol
preferably bears one such polyisobutyl radical. In addition to the
polyisobutyl
radicals, the phenol may also bear, one, two or three shorter-chain
hydrocarbyl
radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, tert-
butyl, vinyl, allyl-, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, n-
heptyl, n-
octyl, tert-octyl-, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, 2-propylheptyl,
n-undecyl,
n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl,
oleyl, linoly1
or linolenyl radicals and/or one, two or three functional groups such as
halogen
atoms, for example chlorine or bromine, nitro groups, cyano groups, carboxyl
groups, carboxylic ester groups or sulfo groups, where the total number of
substituents on the phenol is not more than 5, preferably not more than 4 and
in
particular not more than 3.
In a preferred embodiment, the inventive polytetrahydrobenzoxazines are
obtainable in reaction step (B) from at least one phenol which bears, in the
para
position (4 position) to the hydroxyl group, a C8- to C12-alkyl radical or a
polyisobutyl
radical having 16 to 3000 carbon atoms.
The reaction of the condensation product from reaction step (A) with the at
least
one long-chain-substituted phenol is effected in reaction step (B) at higher
temperatures than in reaction step (A), i.e. at 30 to 120 C, especially at 35
to
105 C, in particular at 40 to 90 C. Preference is given to working at standard
pressure. The reaction is effected advantageously in an inert organic solvent
or a
mixture of such solvent, especially an aromatic hydrocarbon such as toluene,
xylene or a technical mixture of relatively high-boiling aromatic
hydrocarbons, for
example SolvessoTM 100, 150, 200, 150 ND or 200 ND. The reaction time is
typically 1 to 10 hours. The stoichiometric ratio of phenol to diamine used in
reaction step (A) is preferably 1.5 : 1 to 3.0 : 1, especially 1.75 : 1 to
2.75 : 1, in
particular 1.9: 1 to 2.6: 1.
The product obtained in reaction step (B) has, or has predominantly, the
structure
of a bistetrahydrobenzoxazine of the general formula II
:A 02819770 20,,
2
R 0 sR
1
R2
R11110 N
N
R2
R2
0 (II)
in which
x is the number 1, 2 or 3,
5
Ri denotes identical or different Cl- to C3000-hydrocarbyl radicals, where
each
benzene ring bears at least one C6- to C3000-hydrocarbyl radical,
R2 denotes hydrogen or identical or different Ci- to Cll-alkyl radicals, and
A is a bridging member having 1 to 20 carbon atoms,
and ring-opened forms of the bistetrahydrobenzoxazines of the general formula
II
resulting from hydrolysis of one or both tetrahydrooxazine rings, where R1 are
the
substituents of the phenol used, R2 is the radical of the aldehyde used, and A
corresponds to the bridging member A in the general formula for the diamine
H2N-A-N H2.
In the compounds II, it is also possible for different R1 substituents to
occur when
mixtures of different phenols are used in reaction step (B).
A typical example of a bistetrahydrobenzoxazine of the general formula II is
the
compound of the formula Ila reproduced below:
r0
Ri
le 3,N 1
0 (11a)
in which R1 is, for example, tert-octyl, n-nonyl, n-dodecyl or polyisobutyl
having an
Mn of 1000.
Reaction step (C) is undertaken by heating the reaction product from reaction
step
(B) to temperatures distinctly above those of step (B). Preference is given
here to
working at 150 to 250 C, especially at 175 to 230 C, in particular at 190 to
220 C,
and preferably at standard pressure. The heating to the temperature range
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specified is effected for at least 10 minutes, preferably for at least 30
minutes, in
particular for 45 to 120 minutes. The bistetrahydrobenzoxazines II polymerize
essentially with opening of tetrahydrooxazine rings and form a highly branched
¨
but not crosslinked to the extent that it is sparingly soluble or insoluble in
mineral oil
media ¨ two- to three-dimensional polymer system.
The heating of the reaction product from reaction step (B) is effected in
reaction
step (C) advantageously in an inert organic solvent or a mixture of such
solvents,
especially an aromatic hydrocarbon such as toluene, xylene or a technical
mixture
of higher-boiling aromatic hydrocarbons, for example SolvessoTM 100, 150, 200,
150 ND or 200 ND.
A typical example of a polytetrahydrobenzoxazine formed in reaction step (C)
is
reproduced below as the compound of the general formula la:
R1
lei is R1
0 0
N)
1 H
R1 N 01 /
N N
n
0 OH OH HO
R1 0 R1 (la)
The substituents R1 are each as defined above; it is also possible for
different
substituents R1 to occur in the molecule when mixtures of different phenols
are
used in reaction step (B). The serial number n typically assumes values of 2
to 10,
especially 4 to 8.
In the inventive polytetrahydrobenzoxazines, the ends of the side chains
usually still
consist of closed tetrahydrooxazine rings. As a result of hydrolysis of some
or all
tetrahydrobenzoxazine rings still present in the end product, the inventive
polytetrahydrobenzoxazines may, however, also have ring-opened forms. Whether
such a hydrolytic ring opening occurs depends substantially on the boundary
conditions of the polymerization in reaction step (C) ¨ for example the
moisture
content and the presence of compounds with catalytic ring-opening action, such
as
protons or Lewis acids.
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The inventive polytetrahydrobenzoxazines preferably have a number-average
molecular weight (Me) of 700 to 50 000, especially of 1500 to 25 000, in
particular of
2500 to 10 000, and a polydispersity index (PDI) of 1.5 to 7.5, preferably of
2.0 to
5Ø
To modify or improve the efficacy as fuel or lubricant additives, the
polytetrahydrobenzoxazines described can be subsequently quaternized.
Therefore, the present invention also provides quaternized
polytetrahydrobenzoxazines which are obtainable by the reaction steps (A), (B)
and
(C) described, and additionally the reaction step
(D) quaternizing some or all quaternizable amino functions of the
reaction product
from reaction step (C).
The quaternizable amino functions in the polytetrahydrobenzoxazines described
are
the tertiary nitrogen atoms.
Useful quaternizing agents are in principle all compounds suitable as such. In
a
preferred embodiment, the inventive quaternized polytetrahydrobenzoxazines are
obtainable in reaction step (D) by quaternizing with at least one epoxide.
This epoxide is preferably a hydrocarbyl epoxide whose four substitutents are
the
same or different and are each hydrogen or hydrocarbyl radicals, where the
hydrocarbyl radicals each have 1 to 10 carbon atoms and at least one such
hydrocarbyl radical must be present. More particularly, these are aliphatic or
aromatic radicals, for example linear or branched to Clo-alkyl radicals, or
aromatic radicals such as phenyl or Ci- to C4-alkylphenyl.
Suitable such hydrocarbyl epoxides are, for example, aliphatic and aromatic
alkylene oxides, such as especially C2- to C12-alkylene oxides, e.g. ethylene
oxide,
propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene
oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-
butene
oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-
hexene
oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-
pentene
oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide, and
also aromatic-substituted ethylene oxides such as optionally substituted
styrene
oxide, especially styrene oxide or 4-methylstyrene oxide.
In the case of use of epoxides as quaternizing agents, they are usually used
in the
presence of free acids, especially in the presence of free protic acids, such
as in
particular with C1- to C12-monocarboxylic acids, e.g. formic acid, acetic acid
or
:A 02819770 2013-08
13
propionic acid, or C2- to C12-dicarboxylic acids, e.g. oxalic acid or adipic
acid, or
else in the presence of sulfonic acids, e.g. benzenesulfonic acid or
toluenesulfonic
acid, or aqueous mineral acids, e.g. sulfuric acid or hydrochloric acid.
To perform the quaternization, the polytetrahydrobenzoxazine from reaction
step
(C) is admixed typically with at least one epoxide, especially in the
stoichiometric
amounts required to achieve the desired quaternization. Per equivalent of
quaternizable tertiary nitrogen atom, it is possible to use, for example, 0.1
to 1.5
equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent. More
particularly,
however, approximately equimolar proportions of the epoxide are used to
quaternize a tertiary amine group. The temperatures employed here are
typically in
the range from 15 to 90 C, especially from 20 to 80 C or from 30 to 70 C. The
reaction time may be in the region of a few minutes or a few hours, for
example
about 10 minutes up to about 24 hours. The reaction can be effected at a
pressure
of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3 bar, but especially at
approximately standard pressure. More particularly, an inert gas atmosphere,
for
example nitrogen, is appropriate.
If required, the reactants can be initially charged in a suitable inert
organic aliphatic
or aromatic solvent or a mixture of such solvents for the quaternization, or a
sufficient proportion of solvent from reaction step (C) is still present.
Typical
examples of suitable solvents are those of the abovementioned SolvessoTM
series,
and also toluene or xylene.
The present invention also provides a process for preparing
polytetrahydrobenzoxazines, which comprises successively performing the
reaction
steps already described above, namely
(A) reacting at least one diamine of the general formula H2N-A-NH2, in
which the
bridging member A is Cl- to C20-alkylene which may be interrupted by up to
10 oxygen atoms and/or tertiary nitrogen atoms, C2- to C20-alkenylene, CS- to
C20-cycloalkylene, Cs- to Cararylene or C7- to C20-aralkylene with at least
one
C1- to Cu-aldehyde and at least one C1- to C8-alkanol at a temperature of 20
to 80 C with elimination and removal of water, where both the aldehyde and
the alcohol may be used in each case in more than double the molar amount
compared to the diamine;
(B) reacting the condensation product from reaction step (A) with at least
one
phenol which bears at least one long-chain substituent having 6 to 3000
carbon atoms in a stoichiometric ratio to the diamine originally used in step
(A) of 1.2: 1 to 3.5: 1 at a temperature of 30 to 120 C;
:A 02819770 201,
14
(C) heating the reaction product from reaction step (B) to a temperature
of 125 to
280 C for at least 10 minutes.
In a preferred embodiment, a further characterizing feature of this process
for
preparing quaternized polytetrahydrobenzoxazines is that reaction steps (A),
(B)
and (C) and additionally the reaction step also already described in detail
above,
namely
(D) quaternizing some or all quaternizable amino functions of the reaction
product
from reaction step (C),
are performed successively.
The inventive polytetrahydrobenzoxazines can alternatively also be defined by
their
general chemical structure. Accordingly, the present invention provides
polytetrahydrobenzoxazines of the general formula I
HOOR1x HOOR1x HO.R1.
A A
R2 R2 R2 R2
(I)
in which
x is the number 1, 2, 3 or 4, where the values of x may be different on the
different
aromatic rings,
n is an integer from 2 to 10, especially from 4 to 8,
R1 denotes identical or different C1- to C3000-hydrocarbyl radicals, where
each
benzene ring bears at least one C6- to C3000-hydrocarbyl radical,
R2 denotes hydrogen or identical or different C1- to C11-alkyl radicals,
A is a bridging member having 2 to 20 carbon atoms and
Q is the radical of a tetrahydrobenzoxazine unit which is attached via a
nitrogen
atom and which may be present in cyclic form according to the formula
:A 02819770
=
2 1
R
R2
or in ring-opened form resulting from hydrolysis of the tetrahydrooxazine
ring,
where the variables R1, R2 and x are each as defined above. In this formula,
R1 are
5 the substituents of the phenol used in the above-described reaction step
(B), R2 is
the radical of the aldehyde used in the reaction step (A) described above, and
A
corresponds to the bridging member A in the general formula for the diamine
H2N-A-NH2 used in the above-described reaction step (A).
10 Since the bistetrahydrobenzoxazines described, as intermediates and also
as
potential fuel and lubricant additives, are new compounds, the present
invention
likewise provides bistetrahydrobenzoxazines of the general formula II
2
R
R2 R
Rix, N¨A N--,
R2
0 (II)
15 in which
x is the number 1, 2, 3 or 4, where the values of x may be different on the
two
different aromatic rings,
R1 denotes identical or different Cl- to C3000-hydrocarbyl radicals, where
each
benzene ring bears at least one C6- to C3000-hydrocarbyl radical,
R2 denotes hydrogen or identical or different to Cii-alkyl radicals,
A is a bridging member having 2 to 20 carbon atoms,
and ring-opened forms of the bistetrahydrobenzoxazines of the general formula
ll
resulting from hydrolysis of one or both tetrahydrooxazine rings, where R1 are
the
substitutents of the phenol used in the above-described reaction step (B), R2
is the
radical of the aldehyde used in the above-described reaction step (A), and A
corresponds to the bridging member A in the general formula for the diamine
H2N-A-NH2 used in the above-described reaction step (A).
:A 02819770 201,-,
=
16
The inventive polytetrahydrobenzoxazines and quaternized
polytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines are
outstandingly suitable as fuel additives or lubricant additives. Fuels in
which the
inventive polytetrahydrobenzoxazines or quaternized polytetrahydrobenzoxazines
or the inventive bistetrahydrobenzoxazines can be used as a fuel additive here
are
especially gasoline fuels and middle distillate fuels, and here in particular
diesel
fuels and heating oils.
To a very particular degree, the inventive polytetrahydrobenzoxazines and
quaternized polytetrahydrobenzoxazines and the inventive
bistetrahydrobenzoxazines are suitable as a detergent additive for diesel
fuels.
Especially in their capacity as a detergent additive for diesel fuels, the
inventive
polytetrahydrobenzoxazines and quaternized polytetrahydrobenzoxazines and the
inventive bistetrahydrobenzoxazines find use as an additive for reducing the
level of
or preventing deposits in injection systems of direct-injection diesel
engines,
especially in common-rail injection systems, for reducing fuel consumption of
direct-
injection diesel engines, especially of diesel engines with common-rail
injection
systems, and/or for minimizing power loss in direct-injection diesel engines,
especially in diesel engines with common-rail injection systems.
The present invention also provides an additive concentrate which comprises,
in
combination with further fuel additives, especially diesel fuel additives, at
least one
inventive polytetrahydrobenzoxazine or quaternized polytetrahydrobenzoxazine,
or
an inventive bistetrahydrobenzoxazine.
The inventive polytetrahydrobenzoxazines or quaternized
polytetrahydrobenzoxazine or the inventive bistetrahydrobenzoxazines are
present
in the inventive additive concentrate preferably in an amount of 0.1 to 100%
by
weight, more preferably of 1 to 80% by weight and especially of 10 to 70% by
weight, based on the total weight of the concentrate.
The present invention further provides a fuel composition, especially a diesel
fuel
composition, which comprises, in a majority of a customary base fuel,
especially of
a diesel fuel, an effective amount of at least one inventive
polytetrahydrobenzoxazine or quaternized polytetrahydrobenzoxazine or of an
inventive bistetrahydrobenzoxazine.
The present invention further provides a lubricant composition, which
comprises, in
a majority of a customary lubricant formulation, an effective amount of at
least one
:A 02819770 2013-08-03
17
inventive polytetrahydrobenzoxazine or quaternized polytetrahydrobenzoxazine
or
of an inventive bistetrahydrobenzoxazine.
Useful gasoline fuels include all commercial gasoline fuel compositions.
Typical
representatives which shall be mentioned here include the market standard
Eurosuper base fuel to EN 228. Further possible fields of use for the present
invention are also gasoline fuel compositions of the specification according
to
WO 00/47698.
Useful middle distillate fuels include all commercial diesel fuel and heating
oil
compositions. Diesel fuels are typically mineral oil raffinates which
generally have a
boiling range of from 100 to 400 C. These are usually distillates having a 95%
point
up to 360 C or even higher. However, they may also be so-called "Ultra low
sulfur
diesel" or "City diesel", characterized by a 95% point of, for example, not
more than
345 C and a sulfur content of not more than 0.005% by weight, or by a 95%
point
of, for example, 285 C and a sulfur content of not more than 0.001% by weight.
In
addition to the diesel fuels obtainable by refining, whose main constituents
are
relatively long-chain paraffins, those obtainable by coal gasification or gas
liquefaction ["gas to liquid" (GTL) fuels] are suitable. Also suitable are
mixtures of
the aforementioned diesel fuels with renewable fuels such as biodiesel or
bioethanol. Of particular interest at the present time are diesel fuels with a
low
sulfur content, i.e. with a sulfur content of less than 0.05% by weight,
preferably of
less than 0.02% by weight, in particular of less than 0.005% by weight and
especially of less than 0.001% by weight of sulfur. Diesel fuels may also
comprise
water, for example in an amount up to 20% by weight, for example in the form
of
diesel-water microemulsions or as so-called "white diesel".
Heating oils are, for example, low-sulfur or sulfur-rich mineral oil
raffinates or
bituminous coal or brown coal distillates which typically have a boiling range
of from
150 to 400 C. Heating oils may be standard heating oil according to DIN 51603-
1,
which has a sulfur content of from 0.005 to 0.2% by weight, or they are low-
sulfur
heating oils having a sulfur content of from 0 to 0.005% by weight. Examples
of
heating oil include especially heating oil for domestic oil-fired boilers or
EL heating
oil.
The inventive polytetrahydrobenzoxazines or quaternized
polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines can
either
be added to the particular base fuel, especially the gasoline or the diesel
fuel, alone
or in the form of fuel additive packages, for example the so-called diesel
performance packages. Such packages are fuel additive concentrates and
generally comprise, as well as solvents, also a series of further components
as
:A 02819770 2013,
=
18
coadditives, for example carrier oils, cold flow improvers, corrosion
inhibitors,
demulsifiers, dehazers, antifoams, further cetane number improvers, further
combustion improvers, antioxidants or stabilizers, antistats, metallocenes,
metal
deactivators, solubilizers, markers and/or dyes.
In a preferred embodiment, the additized gasoline or diesel fuel comprises, in
addition to the inventive polytetrahydrobenzoxazines or quaternized
polytetrahydrobenzoxazines or inventive bistetrahydrobenzoxazines, as further
fuel
additives, especially at least one (further) detergent additive, referred to
hereinafter
as component (D).
Detergents or detergent additives (D) typically refer to deposition inhibitors
for fuels.
The detergents are preferably amphiphilic substances which have at least one
hydrophobic hydrocarbyl radical having a number-average molecular weight (Me)
of
85 to 20 000, especially of 300 to 5000 and in particular of 500 to 2500, and
at least
one polar moiety which is selected from
(Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one
nitrogen atom having basic properties;
(Db) nitro groups, optionally in combination with hydroxyl groups;
(Dc) hydroxyl groups in combination with mono- or polyamino groups, at least
one
nitrogen atom having basic properties;
(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
(De) sulfo groups or their alkali metal or alkaline earth metal salts;
(Df) polyoxy-C2-C4-alkylene moieties terminated by hydroxyl groups, mono- or
polyamino groups, at least one nitrogen atom having basic properties, or by
carbannate groups;
(Dg) carboxylic ester groups;
(Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino
and/or amido and/or imido groups; and/or
(Di) moieties obtained by Mannich reaction of substituted phenols with
aldehydes
and mono- or polyamines.
:A 02819770 201,
19
The hydrophobic hydrocarbon radical in the above detergent additives, which
ensures the adequate solubility in the fuel oil composition, has a number-
average
molecular weight (Me) of 85 to 20 000, especially of 300 to 5000, in
particular of 500
to 2500. Useful typical hydrophobic hydrocarbyl radicals, especially in
conjunction
with the polar moieties (Da), (Dc), (Dh) and (Di), are relatively long-chain
alkyl and
alkenyl groups, especially the polypropenyl, polybutenyl and polyisobutenyl
radicals
each having Mn = 300 to 5000, especially 500 to 2500, in particular 700 to
2300.
Examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Da) are preferably
polyalkenemono- or polyalkenepolyamines based on polypropene or conventional
(i.e. having predominantly internal double bonds) polybutene or polyisobutene
having Mn = 300 to 5000. When the preparation of the additives proceeds from
polybutene or polyisobutene having predominantly internal double bonds
(usually in
the 13 and y positions), one possible preparative route is by chlorination and
subsequent amination or by oxidation of the double bond with air or ozone to
give
the carbonyl or carboxyl compound and subsequent amination under reductive
(hydrogenating) conditions. The amines used here for the amination may be, for
example, ammonia, monoamines or polyamines such as
dimethylaminopropylamine, ethylenediamine, diethylenetriamine,
triethylenetetramine or tetraethylenepentamine. Corresponding additives based
on
polypropene are described in particular in WO-A-94/24231.
Further preferred additives comprising monoamino groups (Da) are the
hydrogenation products of the reaction products of polyisobutenes having an
average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures
of
nitrogen oxides and oxygen, as described in particular in WO-A-97/03946.
Further preferred additives comprising monoannino groups (Da) are the
compounds
obtainable from polyisobutene epoxides by reaction with amines and subsequent
dehydration and reduction of the amino alcohols, as described in particular in
DE-A-
196 20 262.
Additives comprising nitro groups (Db), optionally in combination with
hydroxyl
groups, are preferably reaction products of polyisobutenes having an average
degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or
mixtures
of nitrogen oxides and oxygen, as described in particular in WO-A-96/03367 and
in
WO-A 96/03479. These reaction products are generally mixtures of pure
nitropolyisobutenes (e.g. a,13-dinitropolyisobutene) and mixed
hydroxynitropolyisobutenes (e.g. a-nitro-13-hydroxypolyisobutene).
I
,
:A 02819770 ,,
Additives comprising hydroxyl groups in combination with mono- or polyamino
groups (Dc) are in particular reaction products of polyisobutene epoxides
obtainable
from polyisobutene having preferably predominantly terminal double bonds and
Mr,
5 = 300 to 5000, with ammonia or mono- or polyamines, as described in
particular in
EP-A-476 485.
Additives comprising carboxyl groups or their alkali metal or alkaline earth
metal
salts (Dd) are preferably copolymers of C2-C40-olefins with maleic anhydride
which
10 have a total molar mass of 500 to 20 000 and some or all of whose
carboxyl groups
have been converted to the alkali metal or alkaline earth metal salts and any
remainder of the carboxyl groups has been reacted with alcohols or amines.
Such
additives are disclosed in particular by EP-A-307 815. Such additives serve
mainly
to prevent valve seat wear and can, as described in WO-A-87/01126,
15 advantageously be used in combination with customary fuel detergents
such as
poly(iso)buteneamines or polyetheramines.
Additives comprising sulfo groups or their alkali metal or alkaline earth
metal salts
(De) are preferably alkali metal or alkaline earth metal salts of an alkyl
20 sulfosuccinate, as described in particular in EP-A-639 632. Such
additives serve
mainly to prevent valve seat wear and can be used advantageously in
combination
with customary fuel detergents such as poly(iso)buteneamines or
polyetheramines.
Additives comprising polyoxy-C2-C4-alkylene moieties (Df) are preferably
polyethers
or polyetheramines which are obtainable by reaction of C2-C60-alkanols, C6-C30-
alkanediols, mono- or di-C2-C3o-alkylamines, Cl-C30-alkylcyclohexanols or C1-
C30-
alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or
butylene oxide per hydroxyl group or amino group and, in the case of the
polyetheramines, by subsequent reductive amination with ammonia, monoamines
or polyamines. Such products are described in particular in EP-A-310 875, EP-A-
356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such
products also have carrier oil properties. Typical examples of these are
tridecanol
butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and
polyisobutenol butoxylates and propoxylates and also the corresponding
reaction
products with ammonia.
Additives comprising carboxylic ester groups (Dg) are preferably esters of
mono-,
di- or tricarboxylic acids with long-chain alkanols or polyols, in particular
those
having a minimum viscosity of 2 mm2/s at 100 C, as described in particular in
DE-
A-38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or
aromatic
acids, and particularly suitable ester alcohols or ester polyols are long-
chain
1
:A 02819770 2017-9A-03
21
representatives having, for example, 6 to 24 carbon atoms. Typical
representatives
of the esters are adipates, phthalates, isophthalates, terephthalates and
trimellitates
of isooctanol, of isononanol, of isodecanol and of isotridecanol. Such
products also
have carrier oil properties.
Additives comprising moieties derived from succinic anhydride and having
hydroxyl
and/or amino and/or amido and/or imido groups (Dh) are preferably
corresponding
derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially
the
corresponding derivatives of polyisobutenylsuccinic anhydride which are
obtainable
by reacting conventional or high-reactivity polyisobutene having M= 300 to
5000
with maleic anhydride by a thermal route or via the chlorinated polyisobutene.
Of
particular interest in this context are derivatives with aliphatic polyamines
such as
especially ethylenediamine, diethylenetriamine, triethylenetetramine or
tetraethylenepentamine. The moieties having hydroxyl and/or amino and/or amido
and/or imido groups are, for example, carboxylic acid groups, acid amides of
monoamines, acid amides of di- or polyamines which, in addition to the amide
function, also have free amine groups, succinic acid derivatives having an
acid and
an amide function, carboximides with monoamines, carboxinnides with di- or
polyamines which, in addition to the imide function, also have free amine
groups, or
diimides which are formed by the reaction of di- or polyamines with two
succinic
acid derivatives. Such fuel additives are common knowledge and are described
especially in US-A-4 849 572.
The detergent additives from group (Dh) are preferably the reaction products
of
alkyl- or alkenyl-substituted succinic anhydrides, especially of
polyisobutenylsuccinic anhydrides, with amines and/or alcohols. These are thus
derivatives which are derived from alkyl-, alkenyl- or polyisobutenylsuccinic
anhydride and have amino and/or amido and/or imido and/or hydroxyl groups. It
is
self-evident that these reaction products are obtainable not only when
substituted
succinic anhydride is used, but also when substituted succinic acid or
suitable acid
derivatives, such as succinyl halides or succinic esters, are used.
The add itized fuel preferably comprises at least one detergent based on a
polyisobutenyl-substituted succinimide. Especially of interest are the imides
with
aliphatic polyamines. Particularly preferred polyamines are ethylenediamine,
diethylenetriamine, triethylenetetramine, pentaethylenehexamine and in
particular
tetraethylenepentamine. The polyisobutenyl radical has a number-average
molecular weight Mn of preferably from 500 to 5000, more preferably from 500
to
2000 and in particular of about 1000.
:A 02819770 ,3
22
Additives comprising moieties (Di) obtained by Mannich reaction of substituted
phenols with aldehydes and mono- or polyamines are preferably reaction
products
of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines
such as ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-
substituted phenols may originate from conventional or high-reactivity
polyisobutene having Mn = 300 to 5000. Such "polyisobutene Mannich bases" are
described especially in EP-A-831 141.
The detergent additives (D) mentioned are preferably used together with the
inventive polytetrahydrobenzoxazines or quaternized polytetrahydrobenzoxazines
or the inventive bistetrahydrobenzoxazines in combination with at least one
carrier
oil.
Suitable mineral carrier oils are the fractions obtained in crude oil
processing, such
as brightstock or base oils having viscosities, for example, from the SN 500 -
2000
class; but also aromatic hydrocarbons, paraffinic hydrocarbons and
alkoxyalkanols.
Likewise useful is a fraction which is obtained in the refining of mineral oil
and is
known as "hydrocrack oil" (vacuum distillate cut having a boiling range of
from
about 360 to 500 C, obtainable from natural mineral oil which has been
catalytically
hydrogenated under high pressure and isomerized and also deparaffinized).
Likewise suitable are mixtures of abovementioned mineral carrier oils.
Examples of suitable synthetic carrier oils are selected from: polyolefins
(poly-
alpha-olefins or poly(internal olefin)s), (poly)esters, (poly)alkoxylates,
polyethers,
aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started
polyetheramines and carboxylic esters of long-chain alkanols.
Examples of suitable polyolefins are olefin polymers having Ma = from 400 to
1800,
in particular based on polybutene or polyisobutene (hydrogenated or
unhydrogenated).
Examples of suitable polyethers or polyetheramines are preferably compounds
comprising polyoxy-C2-C4-alkylene moieties which are obtainable by reacting C2-
C60-alkanols, C6-C30-alkanediols, mono- or di-C2-C30-alkylamines, Cl-C30-
alkylcyclo-
hexanols or C1-C30-alkylphenols with from 1 to 30 mol of ethylene oxide and/or
propylene oxide and/or butylene oxide per hydroxyl group or amino group, and,
in
the case of the polyetheramines, by subsequent reductive amination with
ammonia,
monoamines or polyamines. Such products are described in particular in EP-A
310
875, EP-A 356 725, EP-A 700 985 and US-A-4,877,416. For example, the
polyetheramines used may be poly-C2-C6-alkylene oxide amines or functional
:A 02819770
23
derivatives thereof. Typical examples thereof are tridecanol butoxylates or
isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol
butoxylates and propoxylates, and also the corresponding reaction products
with
ammonia.
Examples of carboxylic esters of long-chain alkanols are in particular esters
of
mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as
described in
particular in DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may
be
aliphatic or aromatic acids; suitable ester alcohols or polyols are in
particular long-
chain representatives having, for example, from 6 to 24 carbon atoms. Typical
representatives of the esters are adipates, phthalates, isophthalates,
terephthalates
and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for
example di(n- or isotridecyl) phthalate.
Further suitable carrier oil systems are described, for example, in DE-A 38 26
608,
DE-A 41 42 241, DE-A 43 09 074, EP-A 0 452 328 and EP-A 0 548 617.
Examples of particularly suitable synthetic carrier oils are alcohol-started
polyethers
having from about 5 to 35, for example from about 5 to 30, C3-C6-alkylene
oxide
units, for example selected from propylene oxide, n-butylene oxide and
isobutylene
oxide units, or mixtures thereof. Nonlimiting examples of suitable starter
alcohols
are long-chain alkanols or phenols substituted by long-chain alkyl in which
the long-
chain alkyl radical is in particular a straight-chain or branched C6-C18-alkyl
radical.
Preferred examples include tridecanol and nonylphenol.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, as
described in
DE-A 101 02913.
Preferred carrier oils are synthetic carrier oils, particular preference being
given to
polyethers.
The inventive fuel composition comprises the inventive
polytetrahydrobenzoxazines
or quaternized polytetrahydrobenzoxazines or the inventive
bistetrahydrobenzoxazines in an amount of typically 10 to 2000 ppm by weight,
more preferably of 20 to 1000 ppm by weight, even more preferably of 30 to 500
ppm by weight and especially of 40 to 200 ppm by weight, z. B. von 50 to 150
ppm
by weight.
When the inventive polytetrahydrobenzoxazines or quaternized
polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines are
added
to the fuel in combination with one or more (further) detergent additives from
group
:A 02819770 291,
24
(D), the total amount of these two additive types is typically 10 to 3000 ppm
by
weight, more preferably from 20 to 1500 ppm by weight, even more preferably
from
30 to 1000 ppm by weight and especially from 40 to 500 ppm by weight, for
example from 50 to 300 ppm by weight.
When a carrier oil is used in addition, it is added to the inventive additized
fuel in an
amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to
500 ppm by weight and in particular from 20 to 100 ppm by weight.
Cold flow improvers suitable as further coadditives are, for example,
copolymers of
ethylene with at least one further unsaturated monomer, e.g. ethylene-vinyl
acetate
copolymers.
Corrosion inhibitors suitable as further coadditives are, for example,
succinic esters,
in particular with polyols, fatty acid derivatives, for example oleic esters,
oligomerized fatty acids and substituted ethanolamines.
Demulsifiers suitable as further coadditives are, for example, the alkali
metal and
alkaline earth metal salts of alkyl-substituted phenol- and
naphthalenesulfonates
and the alkali metal and alkaline earth metal salts of fatty acid, and also
alcohol
alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-
butylphenol
ethoxylates or tert-pentylphenol ethoxylates, fatty acid, alkylphenols,
condensation
products of ethylene oxide and propylene oxide, e.g. ethylene oxide-propylene
oxide block copolymers, polyethyleneimines and polysiloxanes.
Dehazers suitable as further coadditives are, for example, alkoxylated phenol-
formaldehyde condensates.
Antifoams suitable as further coadditives are, for example, polyether-modified
polysiloxanes.
Cetane number and combustion improvers suitable as further coadditives are,
for
example, alkyl nitrates, e.g. cyclohexyl nitrate and especially 2-ethylhexyl
nitrate,
and peroxides, e.g. di-tert-butyl peroxide.
Antioxidants suitable as further coadditives are, for example, substituted
phenols,
e.g. 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and also
phenylenediamines, e.g. N,N'-di-sec-butyl-p-phenylenediamine.
Metal deactivators suitable as further coadditives are, for example, salicylic
acid
derivatives, e.g. N,N'-disalicylidene-1,2-propanediamine.
=
02819770 9rmsmsn
Suitable solvents, especially for fuel additive packages, are, for example,
nonpolar
organic solvents, especially aromatic and aliphatic hydrocarbons, for example
toluene, xylenes, "white spirit" and the technical solvent mixtures of the
5 designations Shellsol (manufacturer: Royal Dutch / Shell Group), Exxol
(manufacturer: ExxonMobil) and Solvent Naphtha. Also useful here, especially
in a
blend with the nonpolar organic solvents mentioned, are polar organic
solvents, in
particular alcohols such as 2-ethylhexanol, decanol and isotridecanol.
10 When the coadditives and/or solvents mentioned are used in addition in
gasoline or
diesel fuel, they are used in the amounts customary therefor.
The inventive polytetrahydrobenzoxazines and quaternized
polytetrahydrobenzoxazines and the inventive bistetrahydrobenzoxazines are
also
15 particularly advantageously suitable as a lubricant additive. Lubricants
or lubricant
compositions are intended to refer here to motor oil, lubricant oils,
transmission oils
including manual and automatic oils, and related liquid compositions which
serve to
lubricate mechanically moving parts ¨ usually in metal form. The inventive
polytetrahydrobenzoxazines and quaternized polytetrahydrobenzoxazines and the
20 inventive bistetrahydrobenzoxazines act principally as dispersant
additive and/or as
detergent additive in the lubricant compositions.
The inventive lubricant composition comprises the inventive
polytetrahydrobenzoxazines or quaternized polytetrahydrobenzoxazines or the
25 inventive bistetrahydrobenzoxazines in an amount of typically 0.001 to
20% by
weight, preferably 0.01 to 10% by weight, especially 0.05 to 8% by weight and
in
particular 0.1 to 5% by weight, based on the total amount of the lubricant
composition.
The economically most important lubricant compositions are motor oils, and
also
transmission oils including manual and automatic oils. Motor oils consist
typically of
mineral base oils which comprise predominantly paraffinic constituents and are
produced in the refinery by costly inconvenient workup and purification
processes,
having a fraction of approx. 2 to 10% by weight of additives (based on the
active
substance contents). For specific applications, for example high-temperature
applications, the mineral base oils may be replaced partly or fully by
synthetic
components such as organic esters, synthetic hydrocarbons such as olefin
oligomers, poly-a-olefins or polyolefins of hydrocracking oils. Motor oils
also have to
have sufficiently high viscosities at high temperatures in order to ensure
impeccable
lubrication effect and good sealing between cylinder and piston. Moreover, the
flow
properties of motor oils have to be such that the engine can be started
without any
=
:A 02819770 291"
26
problem at low temperatures. Motor oils have to be oxidation-stable and must
generate only small amounts of decomposition products in liquid or solid form
and
deposits even under difficult working conditions. Motor oils disperse solids
(dispersant behavior), prevent deposits (detergent behavior), neutralize
acidic
reaction products and form a wear protective film on the metal surfaces in the
engine. Motor oils are typically characterized by viscosity classes (SAE
classes).
With regard to their base components and additives, transmission oils
including
manual and automatic oils have a similar composition to motor oils. The force
is
transmitted in the gear system of gearboxes to a high degree through the
liquid
pressure in the transmission oil between the teeth. The transmission oil
accordingly
has to be such that it withstands high pressures for prolonged periods without
decomposing. In addition to the viscosity properties, wear, pressure
resistance,
friction, shear stability, traction and running-in performance are the crucial
parameters here.
In addition to the inventive polytetrahydrobenzoxazines or quaternized
polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines, motor
oils
and transmission oils including manual and automatic oils generally also
comprise
at least one, but usually some or all, of the additives listed below in the
amounts
customary therefor (which are stated in brackets in % by weight, based on the
overall lubricant composition):
= antioxidants (0.1 to 5%):
sulfur compounds, for example reaction products of terpenes (a-pinene), resin
oils or low molecular weight polybutenes with sulfur, dialkyl sulfides,
dialkyl
trisulfides, polysulfides, diaryl sulfides, modified thiols,
mercaptobenzimidazoles,
mercaptotriazines, thiophene derivatives, xanthates, zinc
dialkyldithiocarbamates, thioglycols, thioaldehydes, dibenzyl disulfide,
alkylphenol sulfides, dialkylphenol sulfides or sulfur-containing carboxylic
acids
phosphorus compounds, for example triaryl and trialkyl phosphites, dialkyl 3,5-
di-tert-butyl-4-hydroxybenzylphosphonate or phosphonic acid piperazides
sulfur-phosphorus compounds, for example zinc dialkyldithiophosphates (metal
dialkyldithiophosphates also act as corrosion inhibitors and high-pressure
additives in lubricant oils) or reaction products of phosphorus pentasulfide
with
terpenes (a-pinene, dipentene), polybutenes, olefins or unsaturated esters
phenol derivatives, for example sterically hindered mono-, bis- or
trisphenols,
:A 02819770 2013-0,03
27
sterically hindered polycyclic phenols, polyalkylphenols, 2,6-di-tert-butyl-4-
methylphenol or methylene-4,4'-bis(2,6-di-tert-butylphenol) (phenol
derivatives =
are often used in combination with sulfur-based or amine-based antioxidants)
amines, for example arylamines such as diphenylamine, phenyl-a-
naphthylamine or 4,4'-tetramethyldianninodiphenylmethane
metal deactivators in the narrower sense, for example N-
salicylideneethylamine,
N,N'-disalicylideneethylenediamine, N,N'-disalicylidene-1,2-propanediamine,
triethylenediamine, ethylenediaminetetraacetic acid, phosphoric acid, citric
acid,
glycolic acid, lecithin, thiadiazole, imidazole or pyrazole derivatives
= viscosity index improvers (0.05 to 10%), for example: polyisobutenes
having a
molecular weight of typically 10 000 to 45 000, polymethacrylates having a
molecular weight of typically 15 000 to 100 000, homo- and copolymers of 1,3-
dienes such as butadiene or isoprene having a molecular weight of typically
80 000 to 100 000, 1,3-diene-styrene copolymers having a molecular weight of
typically 80 000 to 100 000, maleic anhydride-styrene polymers in esterified
form having a molecular weight of typically 60 000 to 120 000, star-shaped
polymers with block-like structure by virtue of units composed of conjugated
dienes and aromatic monomers having a molecular weight of typically 200 000
to 500 000, polyalkylstyrenes having a molecular weight of typically 80 000 to
150 000, polyolefins composed of ethylene and propylene or styrene-
cyclopentadiene-norbornene terpolymers having a molecular weight of typically
60 000 to 140 000
= pour point depressants (cold flow improvers) (0.03 to 1%), for example
bicyclic
aromatics such as naphthalene with different long-chain alkyl radicals,
polymethacrylates with 12 to 18 carbon atoms in the alcohol radical, a degree
of
branching between 10 to 30 mol% and an average molecular weight of 5000 to
500 000, long-chain alkylphenols and dialkylaryl phthalates or copolymers of
different olefins
= detergents (HD additives) (0.2 to 4%), for example calcium naphthenates,
lead
naphthenates, zinc naphthenates and manganese naphthenates, calcium
dichlorostearates, calcium phenylstearates, calcium chlorophenylstearates,
sulfonation products of alkylaromatics such as dodecylbenzene, petroleum
sulfonates, sodium sulfonates, calcium sulfonates, barium sulfonates or
magnesium sulfonates, neutral, basic and overbased sulfonates, phenates and
carboxylates, salicylates, metal salts of alkylphenols and alkylphenol
sulfides,
phosphates, thiophosphates or alkenylphosphonic acid derivatives
:A 0281977,
28
= ashless dispersants (0.510 10%), for example Mannich condensates of
alkylphenol, formaldehyde and polyalkylenepolyamines, reaction products of
polyisobutenylsuccinic anhydrides with polyhydroxyl compounds or polyamines,
copolymers of alkyl methacrylates with diethylaminoethyl methacrylate, N-
vinylpyrrolidone, N-vinylpyridine or 2-hydroxyethyl methacrylate or vinyl
acetate-
fumarate copolymers
= high-pressure additives (extreme pressure additives) (0.2 to 2.5%), for
example
chlorinated paraffins with chlorine content 40 to 70% by weight, chlorinated
fatty
acid (especially having trichloromethyl end groups), dialkyl
hydrogenphosphites,
triaryl phosphites, aryl phosphates such as tricresyl phosphate, dialkyl
phosphates, trialkyl phosphates such as tributyl phosphate,
trialkylphosphines,
diphosphoric esters, nitroaromatics, aminophenol derivatives of naphthenic
acid, carbamic esters, dithiocarbamic acid derivatives, substituted 1,2,3-
triazoles, mixtures of benzotriazole and alkylsuccinic anhydride or
alkylmaleic
anhydride, 1,2,4-thiadiazole polymers, morpholinobenzothiadiazole disulfide,
chlorinated alkyl sulfides, sulfurized olefins, sulfurized chloronaphthalenes,
chlorinated alkyl thiocarbonates, organic sulfides and polysulfides such as
bis(4-chlorobenzyl) disulfide and tetrachlorodiphenyl sulfide,
trichloroacrolein
mercaptals or especially zinc dialkyldithiophosphates (ZDDPs)
= friction modifiers (0.05 to 1%), especially polar oil-soluble compounds
which
generate a thin layer on the frictional surface by adsorption, for example
fatty
alcohols, fatty amides, fatty acid salts, fatty acid alkyl esters or fatty
acid
glycerides
= antifoam additives (0.0001 to 0.2%), for example liquid silicones such as
polydimethylsiloxanes or polyethylene glycol ethers and sulfides
= demulsifiers (0.1 to 1%), for example dinonylnaphthalenesulfonates in the
form
of their alkali metal and alkaline earth metal salts
= corrosion inhibitors (also known as metal deactivators) (0.01 to 2%), for
example tertiary amines and salts thereof, imino esters, amide oximes,
dianninomethanes, derivatives of saturated or unsaturated fatty acids with
alkanolamines, alkylamines, sarcosines, imidazolines, alkylbenzotriazoles,
dimercaptothiadiazole derivatives, diaryl phosphates, thiophosphoric esters,
neutral salts of primary n-C8-C18-alkylamines or cycloalkylamines with dialkyl
phosphates having branched Cs-C12-alkyl groups, neutral or basic alkaline
earth
metal sulfonates, zinc naphthenates, mono- and dialkylarylsulfonates, barium
:A 02819770
29
dinonylnaphthalenesulfonates, lanolin (wool fat), heavy metal salts of
naphthenic acid, dicarboxylic acid, unsaturated fatty acids, hydroxy fatty
acids,
fatty acid esters, pentaerythrityl monooleates and sorbitan monooleates, 0-
stearoylalkanolamines, polyisobutenylsuccinic acid derivatives or zinc
dialkyldithiophosphates and zinc dialkyldithiocarbamates
= emulsifiers (0.01 to 1%), for example long-chain unsaturated, naturally
occurring
carboxylic acid, naphthenic acids, synthetic carboxylic acid, sulfonamides, N-
oleylsarcosine, alkanesulfamidoacetic acid, dodecylbenzenesulfonate, long-
chain alkylated ammonium salts such as dimethyldodecylbenzylammonium
chloride, imidazolinium salts, alkyl-, alkylaryl-, acyl-, alkylamino- and
acylaminopolyglycols or long-chain acylated mono- and diethanolamines
= dyes and fluorescence additives (0.001 to 0.2%)
= preservatives (0.001 to 0.5%)
= odor improvers (0.001 to 0.2%).
Typical ready-to-use motor oil compositions and transmission oil, including
manual
and automatic oil, compositions in the context of the present invention have
the
following composition, the data for the additives relating to the active
substance
contents and the sum of all components always adding up to 100% by weight:
= 80 to 99.3% by weight, in particular 90 to 98% by weight of motor oil
base or
transmission oil, including manual and automatic oil, base (mineral base oils
and/or synthetic components) including the fractions of solvent and diluent
for
the additives
= 0.1 to 8% by weight of inventive polytetrahydrobenzoxazines or
quaternized
polytetrahydrobenzoxazines or the inventive bistetrahydrobenzoxazines
= 0.2 to 4% by weight, in particular 1.3 to 2.5% by weight of detergents of
group
(d)
= 0.5 to 10% by weight, in particular 1.3 to 6.5% by weight of dispersants
of
group (e)
= 0.1 to 5% by weight, in particular 0.4 to 2.0% by weight of antioxidants
of
group (a) and/or high-pressure additives of group (f) and/or friction
modifiers
of group (g)
:A 02819770
=
= 0.05 to 10% by weight, in particular 0.2 to 1.0% by weight of viscosity
index
improvers of group (b)
5 = 0 to 2% by weight of other additives of groups (c) and (h) to (n).
The invention will be illustrated in detail with reference to the
nonrestrictive
examples which follow.
10 Preparation examples
Example 1 [reaction step (A)]
250 g (3.37 mol) of isobutanol and 60 g (2.0 mol) of paraformaldehyde were
15 suspended at 20 C in 250 g of cyclohexane. This was followed by the
addition of
30 g (0.50 mol) of 1,2-ethylenediamin. The reaction mixture was heated under
reflux at 40 C under a reduced pressure of 83 mbar for 5 hours. Water
eliminated
was removed azeotropically from the reaction mixture. A conversion of 75% was
determined from the amount of water eliminated. After the cyclohexane solvent
and
20 the excess isobutanol had been distilled off, a product mixture
comprising
compounds Illa, Illb and 111c (in a weight ratio of 1 : 0.7 : 0.4) as main
products was
obtained:
OH
0
HO)
(111a)
0
0
(111b)
:A 02819770 2013-08-03
=
31
HO N N OH
(111c)
Also present in minor amounts in this product mixture are the corresponding
tetrakis-(hydroxymethyl)ethylenediamine etherified with isobutanol on only one
hydroxymethyl moiety, and the corresponding tris(hydroxymethyl)ethylenediamine
etherified with isobutanol on only one hydroxymethyl moiety.
This product mixture shows, in the 1H NMR spectrum (CDCI3, 6 in ppm) the
following significant signals:
for IIla: 0.9 (m, -CH3), 1.83 (m, -CH-(CH3)2), 2.9 (s, -NCH2CH2N-), 3.25 (d, -
OCH2-)
and 4.18 (s, -NCH20-);
for IIlb: 0.9 (m, -CH3), 1.83 (m, -CH-(CH3)2), 3.0 (s, -NCH2CH2N-), 3.25 (d, -
OCH2-)
and 4.3 (s, -NCH20-);
forIllc: 3.7 (s, -NCH2CH2N-) and 3.8 (s, -NCH2N-).
Example 2 [reaction step (B)]
The product mixture prepared in example 1 was dissolved together with 262 g
(1.0 mol) of 4-n-dodecylphenol in 525 g of SolvessoTM 150, and heated to 90 C
for
2 hours. Subsequently, the solvent was distilled off under reduced pressure.
The
result was a bistetrahydrobenzoxazine of the formula Ila (R1 = n-dodecyl)
which
had, in the 1H NMR spectrum (CDCI3, 6 in ppm), the following signals:
0.5-1.6 (m, -(CH2)11CH3), 3.0 (s, -NCH2CH2N-), 4.0 (s, -NCH2-), 4.9 (s, -OCH2N-
),
6.7 (s, aromat. CH, meta position), 6.8 and 7.0 (d, aromat. CH, ortho and meta
position).
Example 3 [reaction step (B)]
The product mixture prepared in example 1 was dissolved together with 265 g
(1.28 mol) of 4-tert-octylphenol in 520 g of toluene, and heated to 40 C for 2
hours.
Subsequently, the solvent was distilled off under reduced pressure. The result
was
a bistetrahydrobenzoxazine of the formula Ila (R1= n-tert-octyl) which had, in
the 1H
NMR spectrum (00013, 6 in ppm), the following signals:
:A 02819770
32
1.3 (s, CH3), 1.7 (s, -CH2-), 3.0 (s, -NCH2CH2N-), 4.0 (s, -NCH2-), 4.9 (s, -
OCH2N-),
6.9 (s, aromat. CH, meta position), 7.1-7.3 (m, aromat. CH, ortho and meta
position).
Example 4 [reaction step (B)]
The product mixture prepared in example 1 was dissolved together with 281 g
(1.29 mol) of 4-n-nonylphenol in 520 g toluene, and heated to 40 C for 2
hours.
Subsequently, the solvent was distilled off under reduced pressure. The result
was
a bistetrahydrobenzoxazine of the formula Ila (R1= n-nonyl) which had, in the
1H
NMR spectrum (CDCI3, 6 in ppm), the following signals:
0.5-1.7 (m, -(CH2)8CH3), 3.0 (s, -NCH2CH2N-), 4.0 (s, -NCH2-), 4.9 (s, -OCH2N-
), 6.7
(s, aromat. CH, meta position), 6.8 and 7.0 (d, aromat. CH, ortho and meta
position).
Example 5 [reaction step (0)]
The bistetrahydrobenzoxazine from example 2 was dissolved in a weight ratio of
1 : 1 in SolvessoTM 150, and heated to 205 C for 1 hour. After the solvent had
been
distilled off under reduced pressure, the result was a
polytetrahydrobenzoxazine of
the formula la (R1 = n-dodecyl, n = approx. 6), which had a number-average
molecular weight (Mw) of 4600 g/mol, a number-average molecular weight (Ma) of
1500 g/mol and a polydispersity index (PDI) of 3.07, and exhibited the
following
signals in the 1H NMR spectrum (CDCI3, 6 in ppm):
0.5-1.6 (m, -(CH2)11CH3), 3.0 (s, -NCH2CH2N-), 4.0 (s, -NCH2-), 4.9 (s, -OCH2N-
),
6.7 (s, aromat. CH, meta position), 6.8 and 7.0 (d, aromat. CH, meta and ortho
position).
Use example
To examine the influence of the compounds described on the performance of
direct-injection diesel engines operated with the inventive fuel composition,
the
power loss was determined based on the official test method CEO F-98-08. The
power loss is a direct measure of formation of deposits in the injectors.
A conventional direct-injection diesel engine with a common-rail system was
used.
For more economical execution of the determinations, a shortened engine run
cycle
was used compared to CEO F-98-08, i.e. 1 x 12 hours of run time compared to
4 x 8 hours of run time interrupted by 3 x 8 hours of soak time of the
original test
:A 02819770 201A-v
V
33
method. In addition, injectors which had already been run in and cleaned were
used. All other test details were fulfilled as in CEC F-98-08.
The fuel used was a commercial diesel fuel from Haltermann (RF-06-03 Batch
12).
To synthetically induce the formation of deposits on the injectors, 2 ppm by
weight
of zinc didodecanoate were added thereto.
The additive used was the compound from example 5.
The table which follows shows the results of the power loss determinations:
Test run No. Detergent additive Dosage Power loss, 12 h
[ppm by weight of [at 4000 rpm]
active substance]
Base value none 4.34%
1 Example 5 150 0.41%
2 Example 5 150 0.71%
