U.S. patent application number 10/469594 was filed with the patent office on 2004-05-13 for emulsifiers, especially based on polyisobutylenamines.
Invention is credited to Hueffer, Stephan, Lange, Arno, Mock-Knoblauch, Cordula, Schurmann, Gregor.
Application Number | 20040092412 10/469594 |
Document ID | / |
Family ID | 7675922 |
Filed Date | 2004-05-13 |
United States Patent
Application |
20040092412 |
Kind Code |
A1 |
Hueffer, Stephan ; et
al. |
May 13, 2004 |
Emulsifiers, especially based on polyisobutylenamines
Abstract
Compounds, in particular those based on polyisobutyleneamines,
are suitable as emulsifiers for water-in-oil emulsions and are used
in particular as additives for fuels and lubricants. The novel
compounds are those of the formula I 1 where R.sup.1 is
unsubstituted or C.sub.1-C.sub.12-alkyl-substituted
C.sub.1-C.sub.8-alkylene or C.sub.2-C.sub.8-alkenylene, R.sup.2 is
linear or branched C.sub.8-C.sub.350-alkyl or
C.sub.8-C.sub.350-alkenyl, R.sup.3 and R.sup.4, independently of
one another, are each H, methyl or ethyl and together have not more
than 2 carbon atoms, R.sup.5 is H, M.sup.+, SO.sub.3H,
SO.sub.3.sup.-M.sup.+, OPO.sub.3H, OPO.sub.3.sup.-M.sup.+ or
C(O)R.sup.7, M.sup.+ is NH.sub.4.sup.+, an alkali metal ion or 0.5
alkaline earth metal ion, R.sup.7 is a linear C.sub.2- to
C.sub.10-hydrocarbon radical substituted by at least one
hydrophilic group and y and z, independently of one another, are
each an integer from 0 to 50, and R.sup.5 is H if y is 0, and
R.sup.6 is H if z is 0.
Inventors: |
Hueffer, Stephan;
(Ludwigshafen, DE) ; Mock-Knoblauch, Cordula;
(Ludwigshafen, DE) ; Schurmann, Gregor;
(Schwetzingen, DE) ; Lange, Arno; (Bad
D?uuml;rkheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
7675922 |
Appl. No.: |
10/469594 |
Filed: |
September 2, 2003 |
PCT Filed: |
February 28, 2002 |
PCT NO: |
PCT/EP02/02197 |
Current U.S.
Class: |
508/551 ;
252/389.22; 252/390; 252/391; 44/371; 44/376; 44/418; 44/419;
44/434; 508/404; 508/425; 508/428; 508/555; 564/138; 564/159;
564/160; 564/166; 564/47; 564/49; 564/503 |
Current CPC
Class: |
C10L 1/191 20130101;
C10L 1/2641 20130101; C10L 10/08 20130101; C09K 23/14 20220101;
C10L 1/2383 20130101; C10L 1/2475 20130101; C10L 10/04 20130101;
C09K 23/16 20220101; C10L 1/2683 20130101; C09K 23/017 20220101;
C10L 1/143 20130101; C09K 23/00 20220101; C10L 1/1985 20130101;
C10L 1/328 20130101; C10L 1/2658 20130101; C10L 1/2387 20130101;
C10L 1/224 20130101; C10L 1/2437 20130101 |
Class at
Publication: |
508/551 ;
508/555; 508/425; 508/428; 508/404; 044/371; 044/376; 044/418;
044/419; 044/434; 564/047; 564/049; 564/159; 564/166; 564/138;
564/160; 564/503; 252/389.22; 252/390; 252/391 |
International
Class: |
C10M 133/16; C10L
001/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 1, 2001 |
DE |
101 09 845.6 |
Claims
We claim:
1. A compound of the formula I 7where R.sup.1 is unsubstituted or
C.sub.1-C.sub.12-alkyl-substituted C.sub.1-C.sub.8-alkylene or
C.sub.2-C.sub.8-alkenylene, preferably unsubstituted
C.sub.2-C.sub.4-alkylene, R.sup.2 is linear or branched
C.sub.8-C.sub.350-alkyl or C.sub.8-C.sub.3-50-alkenyl, preferably
C.sub.22-C.sub.350-polyisobutenyl, R.sup.3 and R.sup.4,
independently of one another, are each H, methyl or ethyl and
together have not more than 2 carbon atoms, R.sup.5 and R.sup.6,
independently of one another, are each H, M.sup.+, SO.sub.3H,
SO.sub.3.sup.-M.sup.+, OPO.sub.3H, OPO.sub.3.sup.-M.sup.+ or
C(O)R.sup.7, M.sup.+ is NH.sub.4.sup.+, an alkali metal ion or 0.5
alkaline earth metal ion, R.sup.7 is a linear
C.sub.2-C.sub.10-hydrocarbon radical substituted by at least one
hydrophilic group and y and z, independently of one another, are
each an integer from 0 to 50, and R.sup.5 is H if y is 0, and
R.sup.6 is H if z is 0.
2. A compound as claimed in claim 1, wherein R.sup.2 is a
polyisobutenyl having a number average molar mass of from 300 to
5000, preferably from 500 to 2300, particularly preferably from 500
to 1000.
3. A compound as claimed in claim 1 or claim 2, where R.sup.5 and
R.sup.6 are each C(O)R.sup.7, wherein R.sup.7 corresponds to the
formula VI 8where n is an integer from 1 to 4.
4. A process for the preparation of a compound (I) as claimed in
any of claims 1 to 3 by reacting dicarboxylic acids
HO.sub.2C--R.sup.1--O.sub.2H with amines R.sup.2--NH.sub.2 and
alkylene oxides of the formula III in a suitable sequence, 9and, if
required, by reacting the compound obtained in this manner with
SO.sub.3, P.sub.4O.sub.10 or compounds R.sup.7C(O)OH and, if
required, then with NH.sub.3 or alkali metal (alkaline earth metal)
salts.
5. A compound of the formula II 10where R.sup.1 is unsubstituted or
C.sub.1-C.sub.12-alkyl-substituted C.sub.1-C.sub.8-alkylene or
C.sub.2- to C.sub.8alkenylene, and R.sup.2 is linear or branched
C.sub.8-C.sub.350-alkyl or C.sub.8-C.sub.350-alkenyl.
6. A compound of the formula IV 11where R.sup.2 is linear or
branched C.sub.8-C.sub.350-alkyl or C.sub.8-C.sub.350-alkenyl,
R.sup.3 and R.sup.4, independently of one another, are each H,
methyl or ethyl and together contain not more than 2 carbon atoms,
and R.sup.5 is H, M+, SO.sub.3H, SO.sub.3.sup.-M.sup.+, OPO.sub.3H,
OPO.sub.3.sup.-M.sup.+ or C(O)R.sup.7, M.sup.+ is NH.sub.4.sup.+,
an alkali metal ion or 0.5 alkaline earth metal ion and R.sup.7 is
a linear C.sub.2-C.sub.10-hydroca- rbon radical substituted by at
least one hydrophilic group.
7. A compound of the formula V 12where R.sup.1 is unsubstituted
C.sub.1-C.sub.12-alkyl-substituted C.sub.1-C.sub.8-alkylene or
C.sub.2-C.sub.8alkenylene, R.sup.2 is linear or branched
C.sub.8-C.sub.350-alkyl or C.sub.8-C.sub.350-alkenyl, R.sup.3 and
R.sup.4, independently of one another, are each H, methyl or ethyl
and together contain not more than 2 carbon atoms, R.sup.5 and
R.sup.6, independently of one another, are each H, M.sup.+,
SO.sub.3H, SO.sub.3.sup.-M.sup.+, OPO.sub.3H,
OPO.sub.3.sup.-M.sup.+ or C(O)R.sup.7, M.sup.+ is NH.sub.4.sup.+,
an alkali metal ion or 0.5 alkaline earth metal ion, and R.sup.7 is
a linear C.sub.2-C.sub.10-hydrocarbon radical substituted by at
least one hydrophilic group.
8. The use of a compound as claimed in any of claims 1 to 3,
preferably of a compound in which R.sup.5 and R.sup.6 are each H,
as an emulsifier in the preparation of water-in-oil emulsions, the
oil being a vegetable, animal or synthetic oil or fat.
9. The use of a compound as claimed in any of claims 1 to 3,
preferably of a compound in which R.sup.5 and R.sup.6 are not H, as
an emulsifier of a fuel in the preparation of water-in-fuel
emulsions.
10. A water-in-fuel emulsion resulting from the use as claimed in
claim 9 and containing from 60 to 95% by weight of fuel, preferably
diesel fuel, from 3 to 35% by weight of water and from 0.2 to 10,
preferably from 0.5 to 5, % by weight of a novel compound as
claimed in any of claims 1 to 3, preferably of a compound in which
R.sup.5 and R.sup.6 are not H, as an emulsifier.
11. An emulsion as claimed in claim 10, wherein, in addition to the
novel compound, one or more further emulsifiers, preferably
sorbitan monooleate, C.sub.13-oxo alcohol ethoxylates or
alkylphenol ethoxylates, are present.
12. A process for the preparation of an emulsion as claimed in
claim 10 or 11, wherein the respective components are mixed with
one another and are emulsified in a manner known per se, preferably
in a mixing nozzle.
13. The use of a compound as claimed in any of claims 1 to 3 as a
surfactant, antiwear additive or lubricity-improving or
corrosion-inhibiting additive in fuels, lubricants, fuel additive
concentrates and lubricant additive concentrates or as a
corrosion-inhibiting additive in aqueous liquids.
14. A fuel, lubricant, fuel additive concentrate, lubricant
additive concentrate or aqueous liquid resulting from the use as
claimed in claim 13 and containing at least one compound as claimed
in any of claims 1 to 3.
Description
[0001] The present invention relates to compounds, in particular
based on polyisobutyleneamines, which are suitable as emulsifiers
for water-in-oil emulsions, processes for the preparation of such
compounds and the emulsions themselves.
[0002] The present invention also relates to the use of such
compounds as additives for fuels and lubricants and as
corrosion-inhibiting additives in aqueous liquids, and fuels,
lubricants, fuel additive concentrates and lubricant additive
concentrates and aqueous liquids containing the novel
compounds.
[0003] Compounds of various types having emulsifying properties are
disclosed in the prior art. Inter alia, derivatives of
polyisobutenyl-substituted succinic anhydride are used in various
applications.
[0004] For example, U.S. Pat. No. 4,225,447 describes water-in-oil
emulsions which are used as lubricants and contain a
polyisobutenyl-substituted succinic anhydride, an alkali (alkaline
earth) metal salt of a polyisobutenyl-substituted succinic acid or
a polyisobutenylsubstituted succinamide as an emulsifier.
[0005] GB-A 2,157,744 discloses drilling fluids which contain both
an emulsifier, i.e. graft or block copolymers of polycarboxylic
acids and polyethylene glycol, and surfactants. The surfactants
used are compounds which are prepared from a
polyisobutenyl-substituted succinic anhydride and polyols,
polyamines, hydroxycarboxylic acids or amino alcohols.
[0006] EP-A 0 156 572 describes the use of anionic surface-active
substances based on polyisobutenyl-substituted succinic acid
derivatives for the preparation of water-in-oil or oil-in-water
emulsions.
[0007] BASF AG's German Application filed on Jan. 25, 2000 and
having the application number 100 03 105.6 describes the use of
alkoxylated polyisobutylenes as emulsifiers in water-in-fuel
emulsions. These alkoxylated polyisobutylenes can be described by
the formula R--(CH.sub.2).sub.n--(O-A).sub.m--OH. Here, R is a
polyisobutylene having a weight average molar mass of from 300 to
2300, preferably from 500 to 2000. A is an alkylene radical of 2 to
8 carbon atoms. m is a number from 1 to 200 which is chosen so that
the alkoxylated polyisobutylene contains from 0.2 to 1.5 alkylene
oxide units, preferably 0.5 alkylene oxide unit, per C.sub.4 unit;
n is either 0 or 1.
[0008] BASF AG's German Application filed on Jul. 28, 2000 and
having the application number 100 36 956.1 describes, inter alia,
the use of amides of the formula R1R.sup.2NR.sup.3 as emulsifiers
in water-in-oil emulsions, where R.sup.3 is an acyl radical of a
mono- or polycarboxylic acid, R.sup.1 is derived, inter alia, from
a poly-1-butylene, poly-2-butylene or isobutylene or a mixture
thereof and R.sup.2 may be a polyalkylenepolyamine or a
polyalkyleneimine radical.
[0009] In addition to emulsifiers, friction-reducing additives for
fuels and lubricants are also disclosed in the prior art.
[0010] Thus, U.S. Pat. No. 5,858,029 describes friction-reducing
additives for fuels and lubricants, in particular compounds of the
formula R.sup.1(--O(R.sup.2)--).sub.aNH(CO)--R.sup.3--OH, where
R.sup.1 is C.sub.1- to C.sub.60-alkyl, R.sup.2 is C.sub.1- to
C.sub.4-alkylene, a is an integer from 1 to 12 and R.sup.3 is
C.sub.1- to C.sub.4-alkylene or substituted alkylene or
cycloalkylene, being used as friction-reducing additives. In
addition, polyisobutenyl-substituted succinimides may be present as
dispersants and polyalkyleneamines, such as polyisobutyleneamines,
may be present as surfactants.
[0011] The abovementioned compounds disclosed in the prior art have
various disadvantages with regard to preparation and/or product
properties. In the case of some compounds, the synthesis gives rise
to different yields of byproducts which--unless they are
removed--can make it more difficult to establish a constant
viscosity of the emulsifier. Disadvantages can also occur in the
preparation of emulsions: frequently, the emulsions have
insufficeint stability so that phase separation occurs during
storage. The emulsifiers used must therefore be employed in high
concentrations in order to permit the formation of a stable
emulsion.
[0012] There is therefore a need for compounds which can be used as
emulsifiers and do not have said disadvantages. Particularly in the
area of water-in-fuel emulsions, emulsifiers which produce
relatively stable emulsions and additionally permit fuel combustion
which is as complete as possible and substantially residue-free are
required.
[0013] It is an object of the present invention to provide further
compounds which can be used as emulsifiers in oil-in-water and
water-in-oil emulsions.
[0014] We have found that this object is achieved by compounds of
the formula I, 2
[0015] where R.sup.1 is unsubstituted or
C.sub.1-C.sub.1-2-alkyl-substitut- ed C.sub.1-C.sub.8-alkylene or
C.sub.2-C.sub.8-alkenylene,
[0016] R.sup.2 is linear or branched C.sub.8-C.sub.350-alkyl or
C.sub.8-C.sub.350-alkenyl,
[0017] R.sup.3 and R.sup.4, independently of one another, are each
H, methyl or ethyl, and R.sup.3 and R.sup.4 together have not more
than 2 carbon atoms,
[0018] R.sup.5 and R.sup.6, independently of one another, are each
H, M.sup.+, SO.sub.3H, SO.sub.3.sup.-M.sup.+, OPO.sub.3H,
OPO.sub.3.sup.-M.sup.+ or C(O)R.sup.7,
[0019] M.sup.+ is NH.sub.4.sup.+, an alkali metal ion or 0.5
alkaline earth metal ion,
[0020] R.sup.7 is a linear C.sub.2-C.sub.10-hydrocarbon radical
substituted by at least one hydrophilic group and
[0021] y and z, independently of one another, are each an integer
from 0 to 50 and
[0022] R.sup.5 is H if y is 0, and R.sup.6 is H if z is 0.
[0023] The novel compounds (I) can be used as emulsifiers in
water-in-oil emulsions. The fact that frequently lower
concentrations than with the use of conventional emulsifiers are
required for producing stable emulsions is an advantage. If the
novel compounds are used in oil-in-water emulsions, stable vesicles
can be produced under the action of ultrasound.
[0024] The novel compounds can also be used in a variety of ways,
for example as additives in fuels and lubricants, as
corrosion-inhibiting additives in aqueous liquids and as
dispersants for pigments, such as TiO.sub.2.
[0025] The present invention also relates to processes for the
preparation of the compounds (I). These processes are shown
schematically in FIG. 1.
[0026] FIG. 1: Processes for the preparation of compounds (I) where
R.sup.5=R.sup.6=H.
[0027] Suitable reaction conditions for the amidation of the
dicarboxylic acids HO.sub.2C--R.sup.1--CO.sub.2H with the amines
R.sup.2--NH.sub.2 (FIG. 1, Reaction step a1) to give bisamides (II)
are known to a person skilled in the art or can be determined by a
few preliminary experiments.
[0028] The dicarboxylic acids and amines can be reacted with one
another both in organic solvents and in the absence of a solvent.
Suitable organic solvents are, for example, Solvesso.RTM. 150 from
Shell and isododecane.
[0029] In a preferred embodiment of the process, the reaction is
carried out under reduced pressure, for example at from 5 to 50
mbar, and the resulting water is distilled off continuously during
the reaction. Purification of the resulting bisamides (II)--before
further reaction--is generally unnecessary.
[0030] The bisamide (II) thus obtainable is then reacted with
alkylene oxides (III) by a process known to a person skilled in the
art to give alcohols of the formula I in which R.sup.5 and R.sup.6
are each H (FIG. 1, Reaction step a2). This reaction is carried out
in general in the presence of a conventional basic catalyst, such
as KOH, NaOH, NaOMe, KtBuO, Ca(OH).sub.2 or CaO, or a support
catalyst, such as a zeolite.
[0031] Hydrophilic groups can be introduced into the novel
compounds (I) thus obtainable, in which R.sup.5 and R.sup.6 are
each H. For example, the novel compounds (I) in which R.sup.5 and
R.sup.6 are each H can be sulfated with SO.sub.3 to give sulfuric
esters ((I) where R.sup.5=R.sup.6=SO.sub.3H) reacted with
P.sub.4O.sub.10 to give phosphoric esters ((I) where
R.sup.5=R.sup.6=OPO.sub.3H) or reacted with compounds
HO.sub.2C--R.sup.7 to give esters ((I) where
R.sup.5=R.sup.6=C(O)R.sup.7), said reactions being carried out by
standard processes as described, for example, in Falbe (Editor),
Surfactants in consumer products 1986, Springer Verlag Berlin, page
54 et seq., in the US Application with the application number 60
160 212 of Oct. 19, 1999 and in the PCT Application with the
application number PCT/EP/00/09923.
[0032] By adding NH.sub.3 or suitable alkali (alkaline earth) metal
salts, such as alkali (alkaline earth) metal hydroxides, the
corresponding sulfates (I) where
R.sup.5=R.sup.6=SO.sub.3.sup.-M.sup.+, or phosphates (I) where
R.sup.5=R.sup.6=OPO.sub.3M.sup.+, where M.sup.+ is NH.sub.4.sup.+,
an alkali metal ion or 0.5 alkaline earth metal ion, can be
prepared from the sulfuric esters and phosphoric esters,
respectively.
[0033] Alternatively (FIG. 1, Reaction steps b1, b2 and b3),
compounds (I) in which R.sup.5 and R.sup.6 are each H can be
prepared by first reacting amines R.sup.2--NH.sub.2 with alkylene
oxides (III) to give alcohols of the formula IV. Dicarboxylic acids
HO.sub.2C--R.sup.1--CO.sub.2H are then reacted with the alcohols
(IV), in general under the same reaction conditions which are
applied to the reaction of the dicarboxylic acids
HO.sub.2C--R.sup.1--CO.sub.2H with the amines R.sup.2--NH.sub.2.
The resulting bisamides of the formula V where R.sup.5=R.sup.6=H
can be reacted with alkylene oxides III to give compounds (I) in
which R.sup.5 and R.sup.6 are each H. Hydrophilic groups can be
introduced into the bisamides of the formula V where
R.sup.5=R.sup.6=H also directly, as described in the preceding
section.
[0034] Dicarboxylic acids HO.sub.2C--R.sup.1--CO.sub.2H in which
R.sup.1 is C.sub.1-C.sub.8-alkylene or C.sub.2-C.sub.8-alkenylene
and is unsubstituted or substituted by C.sub.1-C.sub.12-alkyl are
used. In the present invention, the term alkenylene also includes
polyunsaturated bivalent hydrocarbon radicals R.sup.1.
[0035] Suitable dicarboxylic acids are, for example, malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid and sebacic acid, which may carry
C.sub.1-C.sub.12-alkyl groups in any desired position. The use of
unsubstituted dicarboxylic acids is preferred. Among these,
succinic acid, glutaric acid, adipic acid, pimelic acid or suberic
acid is preferably used, particularly preferably succinic acid,
glutaric acid or adipic acid.
[0036] In general, amines R.sup.2--NH.sub.2 in which R.sup.2 is
linear or branched C.sub.8-C.sub.350-alkyl or
C.sub.8-C.sub.350-alkenyl are suitable for the preparation of
compounds (1) in which R.sup.5 and R.sup.6 are each H. Here,
alkenyl also includes polyunsaturated hydrocarbon radicals
R.sup.2.
[0037] Amines R.sup.2--NH.sub.2 in which R.sup.2 is
C.sub.22-C.sub.350-polyisobutenyl are preferably used.
[0038] Polyisobutyleneamines R.sup.2--NH.sub.2 where R.sup.2 is
C.sub.22-C.sub.350-polyisobutenyl are prepared from the
corresponding polyisobutylenes by standard processes, as described,
for example, in DE-A 196 20 262, EP-A 0 244 616 and WO-A 97/03946.
The amount of amino groups can be determined by titration with HCl
and then converted into mg KOH per g of substance. The amount of
amino groups per unit weight of substance is then the amine number.
In general, polyisobutylenes which have a number average molecular
weight from 300 to 5000, preferably from 500 to 2300, particularly
preferably from 500 to 1000, are used for the preparation of the
polyisobutyleneamines.
[0039] Among the polyisobutylenes having a number average molecular
weight within said ranges, those which have a high content of
vinylidene groups are preferably used. In the context of the
present invention, this is understood as meaning an amount of
.gtoreq.70, preferably .gtoreq.80, particularly preferably
.gtoreq.85, mol % of vinylidene groups.
[0040] Those polyisobutylenes which have a number average molecular
weight within the abovementioned ranges, a high content of
vinylidene groups and a uniform polymer skeleton structure are
particularly preferably used. Examples of polyisobutylenes having a
uniform polymer skeleton structure are those polyisobutylenes which
are composed of at least 85, preferably at least 90, particularly
preferably at least 95, % by weight of isobutylene units.
[0041] Polyisobutylenes having a number average molecular weight
within said ranges, a high content of vinylidene groups and a
uniform skeleton structure may furthermore have a polydispersity of
.ltoreq.2.5, preferably .ltoreq.2.0. Polydispersity is understood
as meaning the quotient M.sub.w/M.sub.n of weight average molecular
weight M.sub.w and number average molecular weight M.sub.n. The
polydispersity is a measure of the molecular weight distribution of
a polymer.
[0042] Polyisobutylenes which have a number average molecular
weight within said ranges, are composed substantially of
isobutylene units and have a high content of vinylidene groups are
obtainable, for example, under the trade name Glissopal.RTM. from
BASF AG, such as Glissopal.RTM. 1000 having an M.sub.n of 1000,
Glissopal.RTM. V 33 having an M.sub.n of 550 and Glissopal.RTM.
2300 having an M.sub.n of 2300.
[0043] Examples of commercially available polyisobutyleneamines are
the compounds obtainable under the trade name Kerocom.RTM. PIBA
from BASF AG.
[0044] Examples of suitable alkylene oxides (III) are ethylene
oxide, propylene oxide, 1-butylene oxide and 2-butylene oxide.
Ethylene oxide and propylene oxide are preferably used.
[0045] Compounds in which R.sup.7 is a linear
C.sub.2-C.sub.10-hydrocarbon radical substituted by at least one
hydrophilic group are used for R.sup.7--CO.sub.2H. The term
C.sub.2-C.sub.10-hydrocarbon radical includes
C.sub.2-C.sub.10-aLkyl, C.sub.2-C.sub.10-alkenyl and
C.sub.7-C.sub.10-alkylaryl. The term hydrophilic groups also
includes positively or negatively charged groups, and the term
alkenyl includes both monounsaturated and polyunsaturated
hydrocarbon radicals. Examples of hydrophilic groups are
--NH.sub.2, --NH.sub.3.sup.+, --NR.sub.3.sup.+ where R is
C.sub.1-C.sub.6-alkyl, --CO.sub.2H, --CO.sub.2.sup.-, OPO.sub.3H
and OPO.sub.3.sup.-. Compounds where R.sup.7 corresponds to the
formula VI where n=1 to 4 are preferably used for
R.sup.7--CO.sub.2H. R.sup.7--CO.sub.2H corresponds, for example, to
amino acids having at least one additional carboxyl group in the
molecule. The use of aspartic acid (n=1) and glutamic acid (n=2) is
particularly preferred. 3
[0046] In addition to L-amino acids, it is also possible to use the
corresponding D-amino acids or mixtures, such as the racemates of
the D- and L-amino acids.
[0047] The novel compounds (I) can be used as emulsifiers in the
preparation of water-in-oil emulsions. The present invention also
relates to its use. It may be necessary to purify these compounds
and their intermediates, for example when these compounds are used
as emulsifiers for water-in-oil emulsions in the cosmetics or
pharmaceutical sector.
[0048] The novel water-in-oil emulsions contain in general from 95
to 60% by weight of oil, from 3 to 35% by weight of water and from
0.2 to 10% by weight of a novel compound of the formula I.
[0049] For water-in-oil emulsions in which the oil phase is formed
by a vegetable, animal or synthetic oil or fat, novel compounds of
the formula I are used. Compounds of the formula I in which R.sup.5
and R.sup.6 are each H are preferably used. Such water-in-oil
emlusions are used, for example, in the cosmetics or pharmaceutical
sector.
[0050] Examples of vegetable, animal or synthetic oils or fats are
triglycerides and glycol esters (esters of glycolic acid) of lauric
acid, myristic acid, stearic acid, palmitic acid, oleic acid,
linoleic acid and linolenic acid.
[0051] Compounds of the formula I are also used in water-in-oil
emulsions in which the oil phase is formed by a fuel or a light or
heavy heating oil. Compounds of the formula I in which R.sup.5 and
R.sup.6 are not H are preferably used, and compounds of the formula
I in which R.sup.5 and R.sup.6 are each SO.sub.3H,
SO.sub.3.sup.-M.sup.+ or C(O)R.sup.7 are particularly preferably
used. All conventional fuels may be used, for example diesel fuels,
gasoline fuel and kerosene. Diesel fuel is preferably used.
[0052] Novel water-in-fuel emulsions may also contain one or more
C.sub.1-C.sub.4-alcohols and/or monoethylene glycol, in particular
monoethylene glycol. The amount of C.sub.1-C.sub.4-alcohol and/or
monoethylene glycol used is from 5 to 50% by weight, based on the
amount of water. By adding one or more C.sub.1-C.sub.4-alcohols
and/or monoethylene glycol, for example, the temperature range in
which the emulsion is stable can be broadened.
[0053] The novel water-in-fuel emulsions have high stability and
good efficiency during combustion. It is also possible to obtain
good exhaust gas values, the emission of soot and NO.sub.x being
significantly reduced, in particular in diesel engines.
Substantially complete and residue-free combustion without deposits
on the components of the combustion apparatus, for example
injection nozzles, pistons, annular grooves, valves and cylinder
head, can be achieved.
[0054] In addition to the abovementioned constituents, the
water-in-fuel emulsions according to the present invention may have
further components. These are, for example, further emulsifiers,
such as sodium laurylsulfate, quaternary ammonium salts, such as
ammonium nitrate, alkylglycosides, lecithins, polyethylene glycol
ethers and esters, sorbitan oleates, stearates and ricinoleates,
C.sub.13-oxo alcohol ethoxylates and alkylphenol ethoxylates, and
the block copolymers of ethylene oxide and propylene oxide, such as
the Pluronic.RTM. grades from BASF AG. Sorbitan monooleate,
C.sub.13-oxo alcohol ethoxylates and alkylphenol ethoxylates, for
example octyl- and nonylphenol ethoxylates, are preferably used as
further emulsifiers.
[0055] A combination of one or more of the abovementioned further
emulsifiers together with the novel emulsifiers is preferably used
for the novel water-in-fuel emulsions.
[0056] If these further emulsifiers are used, they are employed in
amounts of from 0.5 to 5, preferably from 1 to 2.5, % by weight,
based on the total composition. The amount of this further
emulsifier is chosen so that the total amount of emulsifier, i.e.
novel emulsifier plus further emulsifier, does not exceed the
amount of from 0.2 to 10% by weight stated for the novel emulsifier
alone.
[0057] For the preparation of the novel water-in-oil emulsions, the
chosen novel emulsifier is mixed with the oil, the water and the
further, optionally usable components and is emulsified in a manner
known per se. For example, the emulsification can be effected in a
rotor mixer, by means of a mixing nozzle or by means of an
ultrasound probe. Particularly good results were obtained when a
mixing nozzle of the type disclosed in BASF AG's German
Application, application number 198 56 604 of Dec. 8, 1998, was
used. Water-in-oil emulsions for the cosmetics sector can be
prepared in the same way as water-in-fuel emulsions.
[0058] In addition to their surfactant and emulsifying properties,
the novel compounds (I) also have a lubricity-improving and
corrosion-inhibiting effect. Moreover, they improve the antiwear
behavior of liquids. The novel compounds (I) are therefore used as
additives for lubricants, fuels and aqueous liquids, such as
radiator liquids or drilling and cutting fluids. This use likewise
forms the subject of the present invention.
[0059] The novel compounds (I) can be added directly--together with
other components--to the fuels and lubricants. Alternatively, the
novel compounds (I) can first be mixed with other components to
give fuel or lubricant additive concentrates. These novel fuel or
lubricant additive concentrates can be added in undiluted form or
after dilution with one or more solvents or carrier oils to the
fuels or lubricants. The addition in dilute form is preferred.
[0060] The fuels, lubricants, fuel additive concentrates and
lubricant additive concentrates and aqueous liquids which contain
the novel compounds of the formula I likewise form subjects of the
present invention and are to be explained in more detail below.
[0061] The novel fuels generally contain--in addition to
conventional components--at least one novel compound of the formula
I in an amount of from 10 to 5 000, preferably from 20 to 2000,
ppm, based on the total amount.
[0062] Novel lubricants contain in general from 90 to 99.9,
preferably from 95 to 99.5, % by weight of a liquid, semisolid or
solid lubricant and from 0.1 to 10, preferably from 0.5 to 5, % by
weight of a novel compound (I), based on the total amount.
[0063] Novel fuel additive concentrates and lubricant additive
concentrates contain--in addition to conventional components--at
least one novel compound of the formula I in amounts of from 0.1 to
80, in particular from 0.5 to 60, % by weight, based on the total
weight of the concentrate.
[0064] Conventional components for fuels or fuel additive
concentrates are, for example, additives having a detergent effect,
as described in BASF AG's German Application, application number
100 36 956.1, of Jul. 28, 2000 (page 14 et seq.), in BASF AG's
German Application, application number 100 03 105.6, of Jan. 25,
2000, and in BASF AG's PCT Application having the application
number PCT/EP/01/00496. The additives stated there and further fuel
additives described there and having polar groups likewise form
part of the present application and are hereby incorporated by
reference.
[0065] The novel fuels and fuel additive concentrates may also
contain fuel additives as described, for example, in European
Patent Applications EP-A 0 277 345, 0 356 725, 0 476 485, 0 484
736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 and 0
568 873, German Patent Applications DE-A 39 42 860, 43 09 074, 43
09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845,
196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270 and 196
14 349, and WO-A 96/03479.
[0066] Further conventional components are, for example, further
corrosion-inhibiting additives, antioxidants, stabilizers,
antistatic agents, organometallic compounds, antiwear additives,
markers and cetane number improvers, flow improvers, biocides, such
as glutaraldehyde or glyoxal. The biocides are usually used in an
amount of from 0.01 to 3% by weight, based on the total weight of
the concentrate.
[0067] Examples of further corrosion-inhibiting additives are those
based on ammonium salts of organic carboxylic acids, which salts
tend to form films, or on heterocyclic aromatics for corrosion
protection of nonferrous metals.
[0068] Examples of stabilizers are those based on amines, such as
p-phenylenediamine, dicyclohexylamine or derivatives thereof or on
phenols, such as 2,4-di-tert-butylphenol or
3,5-di-tert-butyl-4-hydroxyph- enylpropionic acid.
[0069] Examples of organometallic compounds are ferrocene or
methylcyclopentadienyl-manganesetricarbonyl.
[0070] Examples of cetane number improvers are organic
C.sub.2-C.sub.10-nitrates, such as 2-ethylhexyl nitrate, and
inorganic cetane number improvers for the aqueous phase, such as
ammonium nitrate. 2-Ethylhexyl nitrate and ammonium nitrate are
preferably used. The cetane number improvers are usually used in an
amount of from 0.05 to 5% by weight, based on the total weight of
the concentrate.
[0071] The suitable solvents for the novel fuel and lubricant
additive concentrates are aliphatic and aromatic hydrocarbons, such
as solvent naphtha, isododecane, mihagol, the fuels and lubricants
themselves and carrier oils.
[0072] Carrier oils, which likewise serve for diluting the fuel
additive concentrates and lubricant additive concentrates, are, for
example, mineral carrier oils (base oils), in particular those of
the viscosity class Solvent Neutral (SN) 100 to 500, and synthetic
carrier oils based on polyolefins, (poly)esters,
(alkylphenol-initiated) polyethers or (aliphatic)
(alkylphenolinitiated) polyetheramines, and carrier oils based on
alkoxylated long-chain alcohols or phenols. Examples of
particularly suitable synthetic carrier oils are those based on
polyolefins, preferably those based on polyisobutylene and on
poly-.alpha.-olefins, having a number average molecular weight of
from 400 to 1800. Polyethylene oxides, polypropylene oxides,
polybutene oxides and mixtures thereof are also suitable carrier
oils. Further suitable carrier oils and carrier oil mixtures are
described, for example, in DE-A 38 38 918, DE-A 38 26 608, DE-A 41
42 241, DE-A 43 09 074, U.S. Pat. No. 4,877,416 and EP-A 0 452
328.
[0073] Novel aqueous liquids contain the novel compounds (I), if
required in combination with further conventional
corrosion-inhibiting additives, in general in an amount of from
about 11 to 10% by weight, based on the total amount.
[0074] The examples which follow illustrate the invention.
EXAMPLES
Example 1
Preparation of the Compounds of the Formula I
[0075] The composition of the compounds prepared is shown in table
1. The polyisobutyleneamine used was Kerocom.RTM. PIBA from BASF
AG.
[0076] Synthesis of the Comounds A1, A2, A3 and A4
[0077] 28 g of adipic acid were added to 750 g of
polyisobutyleneamine (M.sub.n=1000, amine number=36) and heated for
3 hours at 200.degree. C. under reduced pressure. When water no
longer distilled off, the product A1 thus obtained was cooled and
filled.
[0078] A4 was prepared analogously by reacting polyisobutyleneamine
(M.sub.n=550, amine number=36) with adipic acid.
[0079] The reaction of polyisobutyleneamine (M=1000, amine
number=36) with the homologous dicarboxylic acids succinic acid
(product A3) and glutaric acid (product A2) was carried out
analogously. 4
[0080] (where R.sup.2=Polyisobutylenyl)
[0081] Synthesis of compound B 1
[0082] 282 g (about 130 mmol) of compound Al and 3.95 g (35.2 mmol)
of KtBuO were combined and volatile components were removed in a
rotary evaporator at 100.degree. C. and 3 mbar. The reaction
mixture was initially taken in a 2 l metal reactor and then
blanketed three times with 5 bar nitrogen each time. The reactor
contents were heated to 120.degree. C. and 114 g (2.59 mol) of
ethylene oxide were then metered in over 60 minutes until a
pressure of 5 bar had been reached. Stirring was continued until
the pressure remained constant. After cooling and letting down the
pressure in the reactor, compound B1 having a polyethylene glycol
moiety of 5.2% was obtained.
[0083] Synthesis of Compounds C1, C2 and C3
[0084] Compounds B1, B2 and B3 were sulfated in a continuous
process using an SO.sub.3/air mixture having an SO.sub.3 content of
7% by volume. The reaction was carried out at 65.degree. C. in a
vertical falling-film reactor having a length of 95 cm and an
internal diameter of 5 cm. About 400 g/h of compound B1, B2 or B3
as an 80% strength by weight solution in a suitable hydrocarbon,
such as isododecane, heptane or mihagol, were metered into the
reactor from above. The amount of SO.sub.3/air mixture fed to the
falling-film reactor was controlled by means of the acid number of
the sulfated product. The acid number is a measure of the amount of
acid groups, is determined by titration with KOH and is stated in
mg KOH per g of substance. The acid numbers were 22 in the case of
C1, 26 in the case of C2 and 41 in the case of C3. The products
were neutralized batchwise at 25.degree. C. with 25% strength by
weight aqueous NaOH solution. 5
[0085] Synthesis of D1
[0086] 500 g of compound B 1 were dissolved in 500 ml of mihagol,
48 g of L-glutamic acid were added and heating was carried out at
from 160.degree. C. to 180.degree. C. for 90 minutes under reduced
pressure. 6
[0087] Synthesis of D2
[0088] The reaction of compound B 1 with 45 g of L-aspartic acid to
give product D2 was carried out analogously to the synthesis of
D1.
1TABLE 1 Composition of the novel compounds y + z (R.sup.3, R.sup.4
= M.sub.n of H; ethylene R.sup.7--CO.sub.2H Batch R.sup.2--NH.sub.2
R.sup.1 oxide) (amino acid) R.sup.5 = R.sup.6 A1 1000
(CH.sub.2).sub.4 -- -- H A2 1000 (CH.sub.2).sub.3 -- -- H A3 1000
(CH.sub.2).sub.2 -- -- H A4 550 (CH.sub.2).sub.4 -- -- H B1 1000
(CH.sub.2).sub.4 15 -- H B2 1000 (CH.sub.2).sub.2 10 -- H B3 550
(CH.sub.2).sub.4 10 -- H C1 1000 (CH.sub.2).sub.4 15 -- H C2 1000
(CH.sub.2).sub.2 10 -- SO.sup.3-M.sup.+ C3 550 (CH.sub.2).sub.4 10
-- SO.sup.3-M.sup.+ D1 1000 (CH.sub.2).sub.4 15 L-glutamic acid
C(O)R.sup.7 D2 1000 (CH.sub.2).sub.4 15 L-aspartic acid C(O)R.sup.7
D3 550 (CH.sub.2).sub.4 10 L-glutamic acid C(O)R.sup.7
Example 2
Water-in-Fuel Emulsions
[0089] In each case a 1% strength by weight solution of an
emulsifier mixture in diesel fuel was prepared, which emulsifier
mixture was composed of 6 parts of a novel compound (C1, C2, C3,
D1, D2 or D3) and 2 parts of a C.sub.13-oxo alcohol ethoxylate
(Lutensol.RTM. TO 7 from BASF AG), and 2 parts of an alkylphenol
ethoxylate (Emulan.RTM. OP 25). 500 g of this mixture were stirred
with 100 ml of water for 15 minutes at a speed of 24, 000 rpm using
an Ultra-Turrax.RTM. (Jahnke and Kunkel laboratory apparatus
T25).
[0090] For comparison, 6 parts of sorbitan monooleate (S-MAZ 80
from BASF AG) were used instead of the novel compounds.
2TABLE 2 Time to Amount of beginning emulsifier in the of phase
Corrosion Batch Emulsifier mixture separation protection 1 C1 1% 26
d +0 2 C2 1% 28 d +0 3 C3 1% 30 d +0 4 D1 1% >30 d ++ 5 D2 1%
>30 d ++ 6 D3 1% 29 d ++ Comp. 1 S-MAZ 80 1% 6 h -0 Comp. 2
S-MAZ 80 2% 19 d -0
[0091] The results in table 2 show that the water-in-fuel emulsions
of the novel compounds show scarcely any signs of phase separation
after storage for 30 days, whereas phase separation was observed in
the comparative example after only 6 hours. Even when the
concentration of emulsifier was increased from 1 to 2%, based on
the diesel fuel, phase separation was observed after 19 days
(comparative example 2).
Example 3
Use of the Novel Compounds as Corrosion-Inhibiting Additives
[0092] A 20.times.40 mm iron sheet is blasted with 40 .mu.m glass
beads and then--analogously to ASTM D-665--immersed in the
emulsions prepared under Example 1 and stored for 24 hours at
40.+-.1.degree. C. After 24 hours, the iron sheet is investigated
for rust formation. Here, the meanings are as follows:
3 ++ no rust formation; +0 slight rust deposit; -0 rust formation
on more than 25% of the area of the test sheet; -- rust formation
on more than 50% of the test sheet.
[0093] As the results in table 2 show, only slight rust deposition
was observed for the use of the novel compounds as
corrosion-inhibiting additives. In contrast, rust formation
occurred on more than 25% of the area of the test sheet with use of
sorbitan monooleate (comparative examples 1 and 2).
Example 4
Use of the Novel Compounds in Fuels and their Antiwear Behavior
[0094] The novel compounds B3, C1, D1 and D2 were each dissolved
individually in an additivefree diesel fuel (Miro, Karlsruhe). The
concentration of additive in the diesel fuel was 75 ppm. The
assessment of the antiwear behavior was carried out by the HFRR
test (high frequency roller rig test), which was carried out
according to ISO 12156-1. The length of the resulting furrows was
measured and was used as a measure for the wear. The shorter the
furrows, the better was the wear protection of the additive
introduced.
4 TABLE 3 Additive Length of the furrows [.mu.m] No additives 595
Compound B3 440 Compound C1 370 Compound D1 365 Compound D2 390
C.sub.16- to C.sub.22-carboxylic acid mixture (PC30 .RTM. from 420
Elf)
[0095] For comparison, the furrow formation with the use of
additive-free diesel fuel and with the use of diesel fuel to which
C.sub.16- to C.sub.22-carboxylic acid mixture has been added was
observed.
* * * * *