CA2448033A1

CA2448033A1 - Low-molecular and high-molecular emulsifiers, particularly based on polyisobutylene, and mixtures thereof

Info

Publication number: CA2448033A1
Application number: CA002448033A
Authority: CA
Inventors: Stephan Hueffer; Peter Schwab; Gregor Schuermann; Hans Peter Rath; Helmut Mach; Eckard Schauss
Original assignee: Individual
Current assignee: BASF SE
Priority date: 2001-05-22
Filing date: 2002-05-17
Publication date: 2002-11-28
Also published as: WO2002094889A3; CN1511167A; DE10125158A1; WO2002094889A2; JP2004531614A; EP1404726A2; AU2002338977A1; US20040154216A1

Abstract

The invention relates to low-molecular and high-molecular diblock emulsifier s, particularly based on polyisobutylene, of general formulas (Ia) and (Ib), an d to mixtures thereof, whereby: La represents a polyisobutylene group having a numerical average molecular weight Mn ranging from 300 to 1000; Lb represent s a polyisobutylene group having a numerical average molecular weight Mn rangi ng from 2000 to 20000; -A- represents -O-, -N(H)- or N(R1)-; M+ represents H+, an alkali metal ion, 0.5 alkaline-earth metal ions or NH4+, whereby in NH4+, on e or more H's can be substituted by alkyl radicals; R represents a linear or branched saturated hydrocarbon radical, which supports at least one substituent selected from the group consisting of OH, NH2 or NH3+ and optionally supports one or more C(O)H groups while optionally containing one or more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH2 or NH3+ groups, one or more H's can be substituted by alkyl radicals, and; R1 represents a linear or branched saturated hydrocarbon radical, which optionally supports one or more substituents selected from th e group consisting of OH, NH2, NH3+ or C(O)H while optionally containing one o r more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH2 or NH3+ groups, one or more H's can be substituted by alkyl radicals , and the proportion of A-R on the compound of general formula (Ib) equals at least 20 wt. %.

Description

Low molecular weight and high molecular weight emulsifiers, in particular based on polyisobutylene, and mixtures thereof The present invention relates to low molecular weight and high molecular weight compounds, in particular based on polyisobutylene, and mixtures thereof, which are suitable as emulsifiers for water-in-oil emulsions, processes for the preparation of such compounds and the emulsions themselves.
The present invention also relates to the use of such compounds as additives for fuels and lubricants and as corrosion-inhibiting additives in water-containing liquids, and fuels, lubricants, fuel and lubricant additive concentrates and water-containing liquids containing the novel compounds.
The prior art discloses various types of compounds having emulsifying properties. Inter alia, derivatives of succinic anhydride substituted by a polyisobutylenyl group are used in various applications.
Thus, for example US-A 4,225,447 describes water-in-oil emulsions which are used as lubricants and contain a succinic anhydride substituted by an alkylenyl group (such as a polyisobutylenyl group), preferably having a number average molecular weight M" of from 300 to 3 000 g/mol, an alkali metal or alkaline earth metal salt of a succinic acid substituted by an alkenyl group or a succinamide substituted by an alkenyl group, as an emulsifier, if required in combination with the salt of a resin acid.
EP-A 0 156 572 describes the use of surface-active substances based on succinic acid derivatives substituted by polyisobutylenyl groups, preferably having a number average molecular weight M" of from 400 to 5 000, and having an anionic group for the preparation of water-in-oil or oil-in-water emulsions. Suitable anionic groups are phosphate, phosphonate, sulfate, sulfonate and carboxymethyl groups.
The Applicant's German application filed on January 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-(CH2)"-(O-A)m-OH. Here, R is a polyisobutylene having a weight average molar mass of from 300 to 2 300, preferably from 500 to 2 000. 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 per C4 unit, preferably 0.5 alkylene oxide unit per C4 unit; n is either 0 or 1.
The Applicant's German application filed on July 28, 2000 and having the application number 100 36 956.1 describes, inter alia, the use of amides of the formula R1R2NR3 as emulsifiers in water-in-oil emulsions, where R3 is an acyl radical of a mono-or polycarboxylic acid, and Rl may be derived, inter alia, from a poly-1-butylene, poly-2-butylene or poly-isobutylene or mixtures thereof and R2 may be a polyalkylenepolyamine radical or a polyalkyleneimine radical.
WO 00/15740 discloses water-in-fuel emulsions which contain, as emulsifiers, two succinic acid derivatives linked via a linker such as alkanolamine, polyamine or polyol and substituted by hydrocarbon radicals, such as polyisobutylenyl groups, in one embodiment one succinic acid derivative containing a polyisobutylenyl group of 8 to 25 carbon atoms and the other sucinnic acid derivative containing a polyisobutylenyl group of 50 to 400 carbon atoms.
GB-A 2,157,744 discloses drilling fluids which contain both graft or block copolymers of polycarboxylic acids and polyethylene glycol and compounds which are prepared from a succinic anhydride substituted by a polyisobutylenyl group and preferably having a number average molecular weight M~ of from 400 to 5 000, and polyols, preferably polyamines, hydroxycarboxylic acids or amino alcohols.
US 4,708,753 discloses water-in-fuel emulsions which contain, inter alia, mono-or disalts of succinic acid with amines or amine salts of succinic monoesters as emulsifiers. These salts form by reaction of alkanolamines, polyamines, oligoalcohols or polyols with succinic anhydrides which are substituted by CZO-C5~-hydrocarbon radicals, such as polyisobutyenyl groups. In the examples, only those salts of succinic acids or of their monoesters are described which carry a polyisobutylenyl group having a number average molecular weight of 950 to 1 700.
Friction-reducing additives for fuels and lubricants as well as emulsifiers are disclosed in the prior art.
Thus, US 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula Rl-(OR2-)aNH(CO)-R3-OH being used as friction-reducing additives, where Rl is Cl- to Cbo-alkyl, RZ is C~- to C4-alkylene, a is an integer from 1 to 12 and R3 is Cl- to C4-alkylene or substituted alkylene or cycloalkylene. In addition, succinimides substituted by polyisobutylenyl groups may be contained as dispersants and polyalkyleneamines, such as polyisobutyleneamines, as surfactants.
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, byproducts are obtained in the synthesis in various yields and - unless they are removed -can make it difficult to establish a constant viscosity of the emulsifier.
Disadvantages may also arise in the preparation of the emulsions: frequently, the emulsions have insufficient stability, so that phase separation occurs during storage. The emulsifiers used therefore have to be employed in high concentrations in order to permit the formation of a stable emulsion.
There is therefore a need for compounds which can be used as emulsifiers and which do not have the stated disadvantages. Particularly in the area of water-in-fuel emulsions, emulsifiers which produce relatively stable emulsions and additionally permit as far as possible complete and substantially residue-free combustion of the fuel are required.
It is an object of the present invention to provide further compounds which can be used as emulsifiers in water-in-oil emulsions.
We have found that this object is achieved by compounds of the formulae (Ia) and (I6) O O
La Lb ~A-R ~A-R
O O M+
M+
O O
(Ia) (Ib) where La is a polyisobutylenyl group having a number average molecular weight M" of from 300 to 1000, Lb is a polyisobutylenyl group having a number average molecular weight M" of from 2 000 to 20 000, -A- is -O-, -N(H)~ or -N(R~~, M+ is H+ or an alkali metal ion, 0.5 alkaline earth metal ion or NH4+, where one or more H
in NH4+ may be replaced by alkyl, R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH2 and NH3+ and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring -O-and/or secondary amines and/or tertiary amines, where one or more H in the NH2- or NH3+ groups may be replaced by alkyl, and R' is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH2, NH3+ and C(O)H and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, and where one or more H in the NH2- or NH3+ groups may be replaced by alkyl, and the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 20% by weight.
Compounds of the formula (Ia) in which the proportion of the hydrophilic radical A-R has low values, such as from 5.2 to 15.2% by weight, are known per se and are described in GB-A 2,157,744 and US 4,708,753. However, the advantageous properties as an emulsifier, which occur in the case of the novel compounds having an A-R
proportion of Z 20% by weight, are not recognized therein.
The novel compounds can be used both individually and in the form of a mixture as emulsifiers in water-in-oil emulsions. It is possible to produce emulsions which are more stable than with the use of conventional emulsifiers.
In particular, the compounds of the formula (Ib) can be considered as two-block emulsifiers linked via a linker, the lipophilic block La or Lb being linked to the linker succinic acid by a covalent C-C bond and the hydrophilic block R or Rl being linked to said linker via an ester or amide bond.
Preferred compounds of the formula (Ia) are those in which - La is a polyisobutylenyl group having a number average molecular weight M"
of from 350 to 950, in particular from 350 to 650, and/or - La is a polyisobutylenyl group which has a polydispersity of s 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and/or - the proportion of A-R in the compound of the formula (Ia) is at least 25, in particular from 35 to 60, % by weight, and/or - R is composed of [-CH2-CH2-XJ, [-CH(CH3)-CHZ-X] and/or [-CH2-CH(CH3~-X]
units, where X is O or NH.
Preferred compounds of the formula (Ib) are those in which - Lb is a polyisobutylenyl group having a number average molecular weight of from 2 000 to 12 000, in particular from 2 300 to 5 000, and/or - Lb is a polyisobutylenyl group which has a polydispersity of s 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and/or - the proportion of A-R in the compound of the formula (Ib) is at least 25, in particular from 35 to 60, % by weight, and/or - R is composed of [-CHz-CH2-X], [-CH(CH3~CH2-X] and/or [-CHZ-CH(CH3~-X]
units, where X is O or NH.
Particularly preferred compounds of the formula (Ia) or (Ib) are those in which A is -O-and R is a monovalent radical of an oligomer or polymer of ethylene oxide and/or propylene oxide or a monovalent radical of a block copolymer of ethylene oxide and propylene oxide.
Particularly effective emulsifiers are compounds of the formula (Ia) in which La is a polyisobutylenyl group having a number average molecular weight M" of from 350 to 950, in particular from 350 to 650, this polyisobutylenyl group having, if required, a polydispersity of s 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2Ø
It has been found that the total amount of emulsifier for the preparation of stable emulsions can be reduced if the emulsifier used is a mixture containing (a) not more than 99, preferably from 98 to 80, particularly preferably from 97 to 85, %
by weight of at least one compound of the formula (Ia), O
La ~A-R
O M+
O
O
Lb 'A-R
O M+
O
(Ia) (Ib) (b) at least l, preferably from 2 to 20, particularly preferably from 3 to 15, % by weight of at least one compound of the formula (Ib), where La is a polyisobutylenyl group having a number average molecular weight M" of from 300 to 1 000 and Lb is a polyisobutylenyl group having a number average molecular weight M" of from 2 000 to 20 000, -A- is -O-, -N(H}- or -N(Rl~, M+ is H+, an alkali metal ion, 0.5 alkaline earth metal ion or NH4+, where one or more H in NH4+ may be replaced by alkyl, R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH2 and NH3+ and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, and where one or more H in the NH2- or NH3+ groups may be replaced by alkyl, and Rl is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH2, NH3+
and C(O)H and, if required, contains one or more nonneighboring -0- and/or secondary amines and/or tertiary amines, and where one or more H in the NHZ-or NH3+ groups may be replaced by alkyl, and the proportion of A-R in the compound of the formula (Ia) is at least 10% by weight and that in the compound of the formula (Ib) is at least 20% by weight.

Effective emulsifier mixtures are obtained not only with the use of compounds of the formula (Ia) having hydrophilic moieties of at least 20% by weight but also with the use of compounds of the formula (Ia) having hydrophilic moieties of at least 10% by weight.
Preferred novel mixtures are those which - in addition to at least one compound of the formula (Ib) -contain not more than 99, preferably from 98 to 80, particularly preferably from 97 to 85, % by weight of at least one compound of the formula (Ia), where La is a polyisobutylenyl group having a number average molecular weight M" of from 350 to 950, in particular from 350 to 650, and/or the proportion of A-R in the compound of the formula (Ia) is at least 15, preferably at least 20, particularly preferably at least 25, very particularly preferably from 35 to 60, % by weight.
Other preferred novel mixtures are those which - in addition to at least one compound of the formula (Ia) -contain at least 1, preferably from 2 to 20, particularly preferably from 3 to 15, % by weight of at least one compound of the formula (Ib), where Lb is a polyisobutylenyl group having a number average molecular weight M" of from 2 000 to 12 000, in particular from 2 300 to 5 000, and/or the proportion of A-R in the compound of the formula (Ib) is at least 25, in particular from 35 to 60, % by weight.
The present invention also relates to processes for the preparation of compounds of the formula (Ia) or (Ib). Here, polyisobutylene is reacted with fumaryl dichloride, fumaric acid, maleyl dichloride, malefic anhydride or malefic acid, preferably with malefic anhydride or maleyl dichloride, particularly preferably with malefic anhydride, to give succinic acid derivatives of the formula (IIa), (IIb) or (IIc), where La is a polyisobutylenyl group having a number average molecular weight M" of from 300 to 1 000 and Lb is a polyisobutylenyl group having a number average molecular weight Mn of from 2 000 to 20 000.
O O O
~OH
O C~ OH
O p O
(IIa) (IIb) (IIc) g The reaction is carried out by the processes known to a person skilled in the art and, for example, analogously to the processes, described in DE-A 195 19 042, DE-A 43 and DE-A 43 19 672, for the reaction of polyisobutylenes with malefic anhydride.
The number average molecular weight M" of the resulting succinic anhydride derivative substituted by a polyisobutylenyl group - can be characterized by means of the saponification number [mg KOH/g of substance].
The substituted succinic acid derivatives of the formulae (IIa) and (IIb) are then reacted by the process known to a person skilled in the art, with polar reactants ROH or RR1NH, where R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH2 and NH3+ and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring -O-and/or secondary amines and/or tertiary amines, and where one or more H in the NH2-or NH3+
groups may be replaced by alkyl, and Rl is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH2, NH3+ and C(O)H and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, and where one or more H in the NH2- or NH3+ groups may be replaced by alkyl.
The alkyl radicals which may replace the H atoms may be Cl-C4-alkyl.
Examples of suitable polar reactants ROH and RR1NH are alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols and carbohydrates and sugars. Other polar reactants may be ethylene oxide and/or propylene oxide.
The reaction with polyethylene glycol, polypropylene glycol, (block) copolymers thereof, ethylene oxide or propylene oxide is preferred. For the preparation of low molecular weight compounds of the formula (Ia), the reaction with alkanolamines, such as di- or triethanolamine, tris(hydroxymethyl)aminomethane and salts thereof, oligoalcohols, such as sorbitol and pentaerythritol, or carbohydrates and sugars is also preferred. The reaction with tris(hydroxymethyl)aminomethane, choline, sugars and polyethylene glycol is particularly preferred for the preparation of compounds of the formula (Ia).
The amount of the polar reactant is chosen so that the proportion of the hydrophilic radical A-R in the compound of the formula (Ia) or (Ib) is at least 20, preferably 25, particularly preferably from 35 to 60, % by weight. Compounds of the formula (Ia) in which the hydrophilic moiety comprises from 10 to 20% by weight can also be prepared by the processes described. The ratio of the substituted succinic acid derivatives (IIa), (IIb) or (IIc) to the alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols or polyalkylene glycols in the reaction is in general from 1 : (0.75 to 2), preferably from 1 : (0.8 to 1.2), particularly preferably 1 : 1. In the reaction of ethylene oxide and/or propylene oxide, the amount of ethylene oxide and/or propylene oxide is chosen according to the desired chain length of the hydrophilic radical A-R.
Compounds of the formula (Ia) or (Ib) where A is -O- and R is a monovalent radical of an oligomer or polymer of ethylene oxide and/or propylene oxide or a monovalent radical of a block copolymer of ethylene oxide and propylene oxide can be obtained both by reacting polyethylene glycol, polypropylene glycol or (block) copolymers thereof with the substituted succinic acid derivatives (IIa), (IIb) or (IIc) and by reacting ethylene oxide and/or propylene oxide with the substituted succinic acid derivatives (IIa), (IIb) or (IIc).
By reacting the substituted succinic acid derivatives (IIa), (IIb) or (IIc) with said polar reactants, succinic monoesters or succinic monoamides are obtained. When alkanolamines are used, the hydroxyl and/or amino groups react so that in general mixtures of succinic monoesters and succinic monoamides are obtained. If maleyl or fumaryl dichloride is used as a starting material, the C(O)Cl group still present after said reaction steps is hydrolyzed to the COZH group. The free COZH group present in the succinic monoesters and succinic monoamides can then be reacted with NH3, amines or alkali metal or alkaline earth metal salts to give the corresponding amine, alkali metal or alkaline earth metal salts. These salts are compounds of the formula (Ia) or (Ib) where M+ is an alkali metal ion, 0.5 alkaline earth metal ion or NH4+, it being possible for one or more H in NH4+ to be replaced by alkyl. Suitable amines for the salt formation are primary, secondary and tertiary amines which carry linear Cl-C4-alkyl or branched C3-C6-alkyl groups. These alkyl groups may also be substituted by one or more hydroxyl groups. Examples of suitable alkylamines are diethylamine, diisopropylamine, trimethylamine, mono-, di- and triethanolamine and tris(hydroxymethyl)aminomethane.
In general, polyisobutylenes having a number average molecular weight M" of from 300 to 1000, preferably from 350 to 950, particularly preferably from 350 to 650, are used for the preparation of the compounds of the formula (Ia).
In general, polyisobutylenes having a number average molecular weight M" of from 2 000 to 20 000, preferably from 2000 to 12 000, particularly preferably from 2 300 to 5 000, are used for the preparation of the compounds of the formula (Ib).

Among the polyisobutylenes having a number average molecular weight M" in 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 Z 70, preferably a 80, particularly preferably z 85, mol % of vinylidene groups.
Particularly preferably used polyisobutylenes are those which have a number average molecular weight M" in the abovementioned ranges, a high content of vinylidene groups and a uniform polymer skeleton structure. In the context of the present invention, these are understood as meaning polyisobutylenes which are composed of at least 80, preferably at least 90, particularly preferably at least 95, % by weight of isobutylene units.
Polyisobutylenes having a number average molecular weight M~ in said ranges, a high content of vinylidene groups, a uniform skeleton structure and a polydispersity of s 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 20.0 are very particularly preferred. Polydispersity is understood as meaning the quotient MW/M" of weight average molecular weight MW and number average molecular weight M".
Polyisobutylenes which have a number average molecular weight M~ in said ranges, are composed substantially of isobutylene units and have a high content of vinylidene groups are available, for example, under the trade name Glissopal~ from BASF AG, such as Glissopal~ 1000 having an M" of 1000, Glissopal~ V 33 having an M" of 550 and Glissopal~ 2300 having an M" of 2 300.
Examples of suitable alkanolamines, polyamines, oligoalcohols, polyols and polyalkylene glycols which may be used for the preparation of the novel compounds are described in WO 00/15740.
Examples of alkanolamines are monoethanolamine, diethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(2-hydroxypropyl)-N'-(2-aminoethyl)piperazine, tris(hydroxymethyl)-amino-methane, 2-amino-1-butanol, ~3-(2-hydroxyethoxy)ethylamine, glucamine, glucosamine, 4-amino-3-hydroxy-3-methyl-1-butene, N-(3-aminopropyl)-4-(2-hydroxy-ethyl)piperidine, 2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N-(2-hydroxyethyl)-1,3-diaminopropane, 1,3-diamino-2-hydroxypropane, N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxy-ethyl)ethylenediamine, N-(2-hydroxyethoxyethyl)ethylenediamine, 1-(2-hydroxy-ethyl)piperazine, monohydroxypropyl-substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine and N-(3-hydroxybutyl)-tetra-methylen-diamine.

The salts of said alkanolamines may also be used. In these salts, one or more of the H
atoms bonded to N atoms may be replaced by linear Cl-C6-alkyl or branched C3-C6-alkyl groups. Choline may be mentioned by way of example.
Examples of suitable polyamines are polyalkylenepolyamines, such as polymethylenepolyamines, polyethylenepolyamines, polypropylenepolyamines, polybutylenepolyamines and polypentylenepolyamines; cf. also Ethylene Amines in Kirk Othmer's Encyclopedia of Chemical Technology, 2nd Edition, Volume 7, pages 22-37, Interscience Publishers, New York 1965.
Examples of suitable oligoalcohols and polyols are 1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol, 1,2-cyclohexanediol, (mono-, di-)-pentaerythritol, 1,7- and 2,4-heptanediol, 1,2,3-, 1,2,4-, 1,2,5- and 2,3,4-hexanetriol, 1,2,3- and 1,2,4-butanetriol, 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol, 1,10-decanediol, 2-hydroxymethyl-methyl-1,3-propanediol, 2-hydroxymethyl-2-ethyl-1,3-propanediol, sorbitol, mannitol and inositol. Furthermore, CS- and C6-sugars, such as glucose and fructose, are also suitable.
Examples of (oligo)alkylene glycols are (tri-, tetra-, penta- and hexa)ethylene glycol, tri-, tetra-, penta- and hexa)propylene glycol and (tri-, tetra-, penta- and hexa)butylene glycol.
Examples of polyalkylene glycols are polytetrahydrofuran, polyethylene glycol and polypropylene glycol. Preferred polyalkylene glycols are polyethylene glycol and polypropylene glycol. Polyethylene glycol and polypropylene glycol and their block copolymers which have a number average molecular weight M~ of from 300 to 5 000, preferably from 300 to 2 000, particularly preferably from S00 to 1500, are particularly preferably used.
Such polyethylene glycols are available, for example, under the trade name Pluriol~ E
from BASF AG, such as Pluriol~ E 300 having an M" of 300, Pluriol~ E 600 having an M" of 600, Pluriol~ E 4000 having an Mn of 4 000 and Pluriol~ E 5000 having an M~ of 000. Polyethylene-polypropylene glycol block copolymers are available, for example, under the trade name Pluronic~ PE from BASF AG, such as Pluronic~ PE 3500 having an M" of 1 900 and an ethylene oxide content of 50% by weight.
If the novel compounds and/or the novel mixtures are used in oil-in-water emulsions, stable vesicles can be produced. This can be effected, for example, by the action of ultrasound. The novel compounds and/or the novel mixtures can moreover be used in a variety of ways, for example as additives in fuels and lubricants, as corrosion-inhibiting additives in water-containing liquids and as dispersants for inorganic and organic solids dispersions. The novel compounds and/or the novel mixtures can furthermore be used as surfactants for washing and cleaning formulations. The high molecular weight compounds of the formula (Ib) which contain a monovalent radical of a polyethylene glycol as a hydrophilic block are particularly suitable for stabilizing inorganic and organic solids dispersions.
The novel compounds and/or novel mixtures are also suitable as emulsifiers for water-in-oil emulsions in which the oil phase is formed by a vegetable, animal or synthetic oil or fat.
Such emulsions are used in the cosmetics or pharmaceutical sector. Examples of such oils or fats are triglycerides and glycol esters of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.
The novel compounds and/or novel mixtures are particularly advantageously used as emulsifiers for water-in-oil emulsions in which the oil phase is formed by a fuel or a light or heavy heating oil. All conventional fuels may be used, for example diesel fuels, gasoline fuel and kerosene. Diesel fuel is preferably used.
In general, purification of the novel compounds and their intermediates is not necessary;
only in certain applications, for example when these compounds are used as emulsifiers for water-in-oil emulsions in the cosmetics or pharmaceutical sector, purification may be necessary.
The present invention relates to the use of novel compounds and/or novel mixtures as emulsifiers in the preparation of water-in-oil emulsions as well as to the water-in-oil emulsions themselves. Novel water-in-oil emulsions generally contain 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 at least one novel compound and/or one novel mixture.
Novel water-in-fuel emulsions may also contain one or more Cl- to C4-alcohols and/or monoethylene glycol, in particular monoethylene glycol. The amount of Cl-C4-alcohol and/or rnonoethylene glycol used is from 5 to 50% by weight, based on the amount of water. By adding one or more Ct-C4-alcohols and/or monoethylene glycol, for example, the temperature range in which the emulsion is stable can be extended.
The novel water-in-fuel emulsions have high stability and good efficiency during combustion. It is furthermore possible to obtain good exhaust gas values, the emission of soot and NOx being significantly reduced, in particular in the case of diesel engines.
Substantially complete and residue-free combustion without deposits on the assemblies of the combustion apparatus, for example injection nozzles, pistons, annular grooves, valves and cylinder head, can be achieved.

The water-in-fuel emulsions according to the invention may also contain further components in addition to the abovementioned constituents. 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 ricinolates, C13 oxo alcohol ethoxylates and alkylphenol ethoxylates, and block copolymers of ethylene oxide and propylene oxide, such as the Pluronic~ grades from BASF AG. Sorbitan monooleate, C13 oxo alcohol ethoxylates and alkylphenol ethoxylates, for example, octyl- and nonylphenol ethoxylates, are preferably used as further emulsifiers.
A combination of one or more of the abovementioned further emulsifiers together with the novel compounds and/or mixtures thereof is preferably used for the novel water-in-fuel emulsions.
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 does not exceed the stated amount of from 0.2 to 10% by weight for the novel compounds and/or mixtures thereof alone.
For the preparation of the novel water-in-oil emulsions, the novel compounds and/or novel mixtures are mixed with the oil, the water and the further, optionally useful components and are emulsified in a manner known per se. For example, the emulsification can be effected in a rotor mixer or by means of a mixing nozzle or of an ultrasonic probe.
Particularly good results were obtained when a mixing nozzle of the type as disclosed in the Applicant's German application with the application number 198 56 604 of December 8, 1998, was used. Water-in-oil emulsions for the cosmetics sector as well as water-in-fuel emulsions can be prepared.
The novel compounds and/or novel mixtures also have a lubricity-improving and corrosion-inhibiting effect in addition to their surface-active, interface-active and emulsifying properties. In addition, they improve the wear protection behavior of liquids.
The novel compounds and/or novel mixtures are therefore used as additives for lubricants, fuels and water-containing liquids, such as radiator liquids or drilling and cutting fluids.
The present invention also relates to this use.
The novel compounds and/or novel mixtures can be added to the fuels and lubricants directly - together with other components. Alternatively, the novel components and/or novel mixtures can first be mixed with other components to give fuel or lubricant additive concentrates. These novel fuel or lubricant additive concentrates can be added undiluted or in a form diluted with one or more solvents or carrier oils to the fuels or lubricants. The addition in dilute form is preferred.
The fuels, lubricants, fuel additive concentrates and lubricant additive concentrates and water-containing liquids which contain the novel compounds and/or novel mixtures are likewise a subject of the present invention and are to be explained in more detail below.
Novel fuels generally contain - in addition to conventional components - at least one novel compound and/or one novel mixture in an amount of from 10 to 5 000, preferably from 20 to 2 000, ppm, based on the total amount.
Novel lubricants generally contain 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 at least one novel compound and/or one novel mixture, based on the total amount.
Novel fuel additive and lubricant additive concentrates contain - in addition to conventional components - at least one novel compound and/or one novel mixture 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.
Conventional components for fuels or fuel additive concentrates are, for example, additives having a detergent action, as described in the Applicant's German application with the application number 100 36 956.1 of July 28, 2000 (page 14 et seq.), in the Applicant's German application with the application number 100 03 105.6 of January 25, 2000 and in the Applicant's PCT application with the application number PCT/EP/01/00496.
The additives stated there and further fuel additives described there and having polar groups form part of the present application and are hereby incorporated by reference.
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, 0 568 873, the German Patent applications DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270, 196 14 349 and WO-A 96/03479.
Further conventional components are, for example, other corrosion-inhibiting additives, antioxidants, stabilizers, antistatic agents, organometallic compounds, antiwear additives, markers, cetane number improvers, flow improvers and 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.
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 in the case of corrosion protection of nonferrous metals.
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-hydroxyphenylpropionic acid.
Examples of organometallic compounds are ferrocene and methylcyclopenta-dienyl-manganese tricarbonyl.
Examples of cetane number improvers are organic C2-Clo-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.
Suitable solvents for the novel fuel and lubricant additive concentrates are aliphatic and aromatic hydrocarbons, such as solvent naphtha, isododecane, mihagol (an industrial mixture of Clo-C12-paraffins), the fuels and lubricants themselves and carrier oils.
Carrier oils which likewise serve for diluting the fuel and lubricant additive concentrates are, for example, mineral carrier oils (base oils), in particular those of viscosity grade Solvent Neutral (SN) 100 to 500, and synthetic carrier oils based on polyolefins, (poly)esters, (alkylphenol-initiated) polyethers, (aliphatic) (alkyl-phenol-initiated) 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 based on polyisobutylene and on poly-a-olefins, having a number average molecular weight M" of from 400 to 1 800. 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, US 4,877,416 and EP-A 0 452 328.

Novel water-containing liquids contain the novel compounds and/or novel mixtures, if required in combination with further conventional corrosion-inhibiting additives, in general in an amount of from about 1 to 10% by weight, based on the total amount.
The examples which follow illustrate the invention.
Examples Example 1: Preparation of the compounds of the formulae (Ia) and (Ib) The composition of the compounds prepared is shown in table 1.
The polyisobutylene used was Glissopal~ from BASF AG, having a number average molecular weight Mn of from 380 to 8 400, a content of vinylidene terminal groups of > 70 mol %, a polydispersity Mw/Mn of from 1.15 to 1.8 and a polymer skeleton structure comprising more than 85% of isobutylene units. This polyisobutylene serves as a starting material for the synthesis of succinic anhydride substituted by a polyisobutylenyl group (PIBSA = polyisobutylene succinic anhydride).
The polyethylene glycol used was Pluriol~ E from BASF AG, having a number average molecular weight M" of from 300 to 5 000. The polyethylene glycol/polypropylene glycol block copolymer used was Pluronic~ PE 3500 from BASF AG, having a number average molecular weight M" of 1 900 and an ethylene oxide content of 50% by weight.
The solvents used were heptane, mihagol, a mixture of Clo-C12-paraffins from Wintershall, and Solvesso~ 150, a mixture of aromatic hydrocarbons, from ExxonMobil Chemical.
The ion exchanger used was the ion echanger commercially available under the name Ambossol~ from Clariant.
The maleation of the polyisobutylenes to give the corresponding succinic anhydrides was carried out by methods known per se and is described, for example, in DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672.
The compounds obtained were characterized by the acid number, the OH number, the viscosity and/or the IR spectra. The OH number was determined using high-boiling solvents with correction for the solvent, i.e. the OH number of the compounds in the respective solvent was measured and then extrapolated to the pure substance.
In the case of low-boiling solvents, such as heptane, the solvent was removed by distillation and the OH
number of the pure substance was determined.
The viscosities were determined according to DIN 51562.
Table 1: Composition of the compounds of the formula (Ia) or (Ib) Compound Glissopal~ Hydrolysis Polar reactant M" MW/M" number of PIBSA

A 550 1.23 148 HO-CHZ-CH2- 2NH

B 550 1.23 148 (HO-CH~NH2 C 750 1.31 120 D-sorbitol D 380 1.15 210 Pluriol~E 300 E 550 1.23 147 Pluriol~E 300 and F 1000 1.31 95 Pluriol~E 600 G 2300 1.52 40 Pluriol~E 1500 H 5200 1.38 18.3 Pluriol~E 4000 I 8400 1.45 12.0 Pluriol~E 5000 J 1000 1.31 95 HO-CH2-CH2- ZNH

K 1000 1.31 95 Pluronic~ PE

L 550 1.31 148 Choline M 1000 1.31 95 Monoethylene 2300 1.52 40 glycol Preparation of the compound A:
A 1 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 250 g of PIBSA 550 and heated to 90°C. 67 g of diethanolamine are metered via the dropping funnel in the course of 5 minutes. The mixture is heated gradually to 130°C or 170°C. After 2 hours at 170°C, the brown reaction product is filtered at 100°C.
Preparation of the compound B:
A 2 1 four-necked flask with a stirrer, distillation bridge and thermocouple is filled with 525 g of PIBSA 550, 650 g of Solvesso~ 150 and 175 g of trihydroxymethylaminomethane (TRIS). The mixture is heated gradually to 130°C or 170°C. Water liberated is removed by means of a nitrogen stream; the reaction time is 3 hours. The OH number was determined as 250 with correction for solvent.
Preparation of the compound C:
A 1 1 four-necked flask with a stirrer, distillation bridge and thermocouple is filled with 310 g of PIBSA 750 and 60 g of D-sorbitol. The mixture is gradually heated to 160°C or 220°C. Water liberated is removed by means of the nitrogen stream;
after 3 hours at 220°C, dilution is effected with 200 g of mihagol and filtration is carried out while hot. A
yellow, viscous product solution (65%) is obtained.
Preparation of the compound D:
A 2 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 350 g of Pluriol~ E 300 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 650 g of PIBSA 380 in 350 g of heptane is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C. Heptane is distilled off at reduced pressure (350 mbar) during this procedure. After 3 hours at 140°C, a yellow product having a viscosity of 105 mm2/s (100°C) is obtained;
OH number: 70; acid number: 73; IR: intense band at 1 735 cm-1 (ester).
Preparation of the comuound E:
A 2 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 300 g of Pluriol~ E 300 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 750 g of PIBSA 550 in 450 g of heptane is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C . Heptane is distilled off at reduced pressure (350 mbar) during this procedure. After 3 hours at 140°C, 105 g of diethanolamine are added a little at a time at 95°C. After a further 20 minutes at 95°C, the orange-brown product is filtered while hot. OH number:
55; IR: intense band at 1 736 cm-~ (ester).
Preparation of the compound F:
A 2 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 400 g of Pluriol~ E 600 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 790 g of PIBSA 1000 in 450 g of heptane is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C. Heptane is distilled off under reduced pressure (350 mbar) during this procedure.

After 3 hours at 140°C, a yellow product having a viscosity of 1650 mm2/s (100°C) is obtained. OH number: 43; acid number: 40; IR: intense band at 1 734 cm-1 (ester).
Preparation of the compound G:
A 1 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 150 g of Pluriol~ E 1500 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 280 g of PIBSA 2300 in 300 g of mihagol is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C. After 3 hours at 140°C, a yellow, highly viscous product solution is obtained. Viscosity 1750 mm2/s, 100°C; OH number: 9; acid number: 8.1;
IR: band at 1 736 cm 1.
Preparation of the compound H:
A 1 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 150 g of Pluriol~ E 4000 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 250 g of PIBSA 5200 in 300 g of mihagol is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C. After 3 hours at 140°C, a beige wax is obtained. OH number: 4.3; acid number: 3.5; IR: band at 1 736 cm~l (ester).
Preparation of the compound I:
The synthesis is effected analogously to the synthesis of the compound H from PIBSA
(basis: reactive PIB 8400; MW/M" = 1.45) and Pluriol~ E 5000. The product is isolated as cream-colored wax (60% strength in mihagol); IR: 1737 cm~l.
Preparation of the compound J for comparative example 1:
The synthesis is effected analogously to the synthesis of the compound A from PIBSA
1000 (basis: reactive PIB 1000; MW/M" - 1.31) and diethanolamine (cf. also US 4,708,753). The product is isolated as a brown, highly viscous liquid and has a lower hydrophilic content A-R than compound A.

Preparation of the compound K:
The synthesis is effected analogously to the synthesis of the compound F from PIBSA
1000 (basis: reactive PIB 1000; MW/M" = 1.31) and Pluronic~ PE 3500. The product is isolated as an orange-yellow, highly viscous liquid. Viscosity: 2100 mm2/s ;
100°C.
Preparation of the compound L:
A 1 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 75 g of a 45% strength methanolic solution of choline from Fluka and 150 g of mihagol.
Methanol is then removed at 50°C and reduced pressure (50 mbar) (45 minutes). 200 g of PIBSA 550 is metered into this suspension and the mixture is heated to 90°C in the course of 15 minutes. After 60 minutes, the temperature is increased to 170°C
and stirring is carried out for a further two hours. The brown reaction product is filtered at 100°C.
Preparation of the compound M for comparative example 2:
A 1 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 300 g of PIBSA 2300, 200 g of PIBSA 1000 and 200 g of mihagol and is heated to 95°C.
At 95°C, 17.2 g of ethylene glycol are metered. The mixture is heated to 130°C and is stirred at this temperature for three hours. The brown reaction product is filtered at 100°C.
The emulsifier of comparative example 2 was prepared according to the principle of WO 00/15740, example C-1, page 34.
Preparation of the compound N for comparative example 3:
(The preparation was carried out analogously to compound F. However, compound F has a A-R content of 35.3% whereas the hydrophilic moiety A-R accounts for 15.4% in compound N.) A 2 1 four-necked flask with a stirrer, dropping funnel and thermocouple is filled with 100 g of Pluriol~ E 200 and is degassed at 90°C in the course of 30 minutes under reduced pressure. A solution of 590 g of PIBSA 1000 in 450 g of heptane is metered via a dropping funnel at 80°C in the course of 5 minutes. The mixture is gradually heated to 110°C or 140°C. Heptane is distilled off under reduced pressure (350 mbar) during this procedure.
After 3 hours at 140°C, an amber-colored product having a viscosity of 1 450 mm2/s (100°C) is obtained.

Example 2: Preparation of the water-in-fuel emulsions The preparation or the composition of the fuel mixtures is listed in table 2.
The hydrophilic or water-soluble components were dissolved beforehand in the aqueous phase, and lipophilic components in the diesel oil. 500 g of this mixture were homogenized with 100 ml of water in the course of 15 minutes at a speed of 2 400 rpm using an Ultra-Turrax~ (Jahnke and Kunkel laboratory apparatus T25). The preparation of the emulsion on the industrial scale and the engine tests were carried out analogously to DE-A 198 56 604 of the Applicant (filed on December 8, 1998), using a mixing nozzle described there. The pressure in the mixing apparatus was from 50 to 200, preferably 120, bar (before the orifice) at a total conversion of 12 kg/h.
Table 2 (cf. next pa~e)~Composition of the emulsions * The biocide used was either glyoxal or glutaraldehyde.
Novel low molecular weight compounds were used in examples l, 2, 6 and 7, and novel mixtures of low-molecular weight and high-molecular weight compounds were used in examples 3, 4 and 5.
Example 1 2 3 4 5 6 7 Com- Com- Com-parisonparisonparison Compound % b wei ht 1 2 3 A 1.4 - - - 1.5 - - - - -g _ _ _ _ _ _ _ _ _ _ C13 oxo alcohol 0.2 0.2 - - - 0.2 0.30.3 0.3 0.3 ethoxylate having 5 [-CHZ-CHZ-O]
units Alk 1 henol ethox 0.2 - 0.20.3 0.3 - - - - -(ate C _ _ _ 1.3 - - _ _ _ _ D - - 1.5- - - 0.5- - -g _ _ _ _ _ 1.8 - _ _ _ F - 0.3 - _ _ _ _ _ _ _ G - - 0.2- 0.3 - - - - -H _ _ _ _ _ _ _ _ _ _ I _ _ _ 0.4 - _ _ _ _ _ _ _ _ _ _ _ _ 1.8 - _ g _ _ _ _ _ _ 1.0 - _ _ L - 1.6- _ _ _ _ _ _ _ M _ _ _ _ _ _ _ _ 1.7 -N _ _ _ _ _ _ _ _ - 1.7 Diesel 76.376.076.176.276.076.576.276.0 76.1 76.1 Water 20 20 20 15 20 15 20 15 15 15 Methanol - - - 2 - 3 - - - -Eth lene l col - - - 3 - 2 - 5 5 5 Biocide* 0.4 0.40.5 0.3 0.4 - 0.5 0.4 0.4 0.4 NH4N03 1.5 1.51.5 1.5 1.5 1.51.5 1.5 1.5 1.5 Example 3: Investigations into the stability of the water-in-fuel emulsions The size of the water drops was determined physically by laser diffraction (X3,2 values) using a Malvern Mastersizer 2000 from Malvern Instruments GmbH. The method of measurement is described, for example, in Terence Allen, Particle Size Measurement, Volume 1, 5'h Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999.
Depending on the size distribution actually present, further methods, e.g.
dynamic light scattering, single particle count and ultrasound extinction, are suitable in addition to laser light diffraction.
The size of the water drops is a measure of the quality of the emulsion. The smaller the drop size, the better or more stable is the emulsion. The corresponding values for the drop size (X3,2 values) are listed in table 3. Table 3 shows that, with the use of the novel compounds as well as the novel mixtures, some of the emulsions have substantially smaller drop sizes than the comparative emulsions. That the drop size is actually a measure of the stability of the emulsion at room temperature is evident from the stability values determined by storage experiments. The emulsions having larger drop sizes also have a poorer shelf life.
Table 3: Drop size and stability of the water-in-fuel emulsions Example 1 2 3 4 5 6 7 Com-com- com-parisonparisonparison Drop size 2.92.2 1.0 3.12.53.22.7 5.4 6.2 6.8 (X 3,2 value) m Storage test 86 >95 >95 91 89 79 77 61 58 49 (room temperature)*

% emulsion Storage test 91 100 100 89 93 80 82 73 75 69 (70C)**

% emulsion Storage test - 65 - 91 95 89 - 62 64 63 (-20C)**

% emulsion * 12 weeks; ** 1 week The stability of the emulsions was checked in a static storage test at 20°C (for 12 weeks) and additionally with varying temperatures (-20°C and 70°C, for 1 week each). For this purpose, the emulsion was introduced into a graduated 100 ml upright cylinder and its quality was assessed visually under said conditions.
Compared with the use of emulsifiers from the prior art (comparative examples), an improvement in the shelf life which is significant in some cases is to be observed with the use of the novel emulsifiers and mixtures thereof. The evaluation of the storage experiments at -20°C was subsequently carried out at room temperature.
The emulsion according to example 2 is comparatively homogeneous after thawing, even without the addition of an antifreeze (e.g. monoethylene glycol). Otherwise, phase separation, i.e.
breaking of the emulsion, occurred after or even during warming up.
A comparison of the quality of the novel emulsions with that of an emulsion according to WO 00/15740 (example C-1, page 34, comparative example 2) proves that a combination of a low molecular weight component and a higher molecular weight component to give a correspondingly bridged compound leads to a significantly poorer emulsifier than a novel mixture of the isolated compounds.

' 24 Example 4: Use of the novel compounds of the formula (I) as antirust and antiwear additives An iron sheet measuring 20 x 40 mm is blasted with 40 ,um glass beads and then immersed - similarly to ASTM D-665 - in the emulsions prepared under example 2 and stored at 40 ~ 1°C for 24 hours. After 24 hours, the iron sheet is investigated with regard to rust formation. Here:
++ means no rust formation;
+0 means slight rust deposit;
-0 means rust formation over more than 25% of the area of the test sheet;
-- means rust formation over more than 50% of the test sheet.
As shown by the results in table 4, in some cases only a slight rust deposit was observed with the use of the novel compounds as corrosion-inhibiting additives. In contrast, rust formation occurred on more than 50% of the area of the test sheet when C13 oxo alcohol ethoxylate was used.
Example 5: Use of the novel compounds of the formula (I) in fuels and their antiwear behavior In each case the compounds shown in the table were dissolved in a diesel fuel without additives (Miro, Karlsruhe). The concentration of additive in the diesel fuel was 75 ppm.
The antiwear behavior was assessed 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 of the wear. The shorter the furrows, the better was the wear protection of the additive introduced. Diesel fuel without additives was used for comparison. As shown in table 4, the novel compounds provided protection from wear.
Table 4:
Additive Length of the furrowsCorrosion m]

Com ound 380 +0 B

Com ound 490 -0 C

Com ound 315 +0 D

Com ound 295 ++
E

Compound 320 I ++
F I

Com ound 420 +0 G

Com ound 495 -0 J

No additive 605 --

Claims

We claim:

1. A compound of the formula (Ia) or (Ib) where La is a polyisobutylenyl group having a number average molecular weight M" of from 300 to 1000, Lb is a polyisobutylenyl group having a number average molecular weight M' of from 2 000 to 20 000, -A- is -O-, -N(H}- or -N(Rl)-, M+ is H+ or an alkali metal ion, 0.5 alkaline earth metal ion or NH4+, where one or more H in NH4+ may be replaced by alkyl, R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH2 and NH3+ and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, where one or more H in the NH2- or NH3+ groups may be replaced by alkyl, and Rl is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH2, NH3+
and C(O)H and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, and where one or more H in the NH2-or NH3+ groups may be replaced by alkyl, and the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 20%
by weight.

2. The compound as claimed in claim 1, wherein La is a polyisobutylenyl group having a number average molecular weight Mn of from 350 to 950, in particular from 350 to 650, and Lb is a polyisobutylenyl group having a number average molecular weight of from 2 000 to 12 000, in particular from 2 300 to 5 000.

3. The compound as claimed in claim 1 or 2, wherein La and Lb are each a polyisobutylenyl group which has a polydispersity of s 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2Ø

4. The compound as claimed in any of claims 1 to 3, wherein La and Lb are each a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units.

5. The compound as claimed in any of claims 1 to 4, wherein the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 25, in particular from 35 to 60, % by weight.

6. The compound as claimed in any of claims 1 to 5, wherein A is -O- and R is a monovalent radical of an oligomer or polymer of ethylene oxide and/or propylene oxide or a monovalent radical of a block copolymer of ethylene oxide and propylene oxide.

7. A mixture containing (a) not more than 99, preferably from 98 to 80, particularly preferably from 97 to 85, %
by weight of at least one compound of the formula (Ia), (b) at least 1, preferably from 2 to 20, particularly preferably from 3 to 15, % by weight of at least one compound of the formula (Ib), where L a is a polyisobutylenyl group having a number average molecular weight M n of from 300 to 1 000 and L b is a polyisobutylenyl group having a number average molecular weight M a of from 2 000 to 20 000, -A- is -O-, -N(H)- or -N(R1), M+ is H+ or an alkali metal ion, 0.5 alkaline earth metal ion or NH4+, where one or more H in NH4+ may be replaced by alkyl, R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH2 and NH3+ and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, where one or more H in the NH2- or NH3+ groups may be replaced by alkyl, and R1~is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH2, NH3+
and C(O)H and, if required, contains one or more nonneighboring -O- and/or secondary amines and/or tertiary amines, and where one or more H in the NH2-or NH3+ groups may be replaced by alkyl, and the proportion of A-R in the compound of the formula (Ia) is at least 10% by weight and that in the compound of the formula (Ib) is at least 20% by weight.

8. A mixture as claimed in claim 7, wherein the proportion of A-R in the compound of the formula (Ia) is at least 15, preferably at least 20, particularly preferably at least 25, very particularly preferably from 35 to 60, % by weight and/or that in the compound of the formula (Ib) is at least 25, in particular from 35 to 60, % by weight.

9. The mixture as claimed in claim 7 or 8, wherein L a and/or L b are each a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units.

10. A process for the preparation of compounds of the formula (Ia) and (Ib) as claimed in any of claims 1 to 6, in which polyisobutylene is reacted with fumaryl dichloride, fumaric acid, maleyl dichloride, maleic acid or maleic anhydride, the reaction product obtained is reacted with ethylene oxide, propylene oxide, alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols, carbohydrates or sugars and the free carboxyl group present is, if required, converted with NH3, an amine or an alkali metal salt or alkaline earth metal salt into the corresponding salt.

11. ~The use of a compound of the formula (Ia) and/or (Ib) as claimed in any of claims 1 to 6 and/or of a mixture as claimed in any of claims 7 to 9 as a surface-active substance, as an emulsifier, as an antiwear additive, as a lubricity additive or as a corrosion-inhibiting additive in fuels, lubricants or fuel additive and lubricant additive concentrates or as a corrosion-inhibiting additive in water-containing liquids.

12. ~The use as claimed in claim 11, the compound and/or the mixture being used as an emulsifier in the preparation of water-in-oil emulsions, in particular of water-in-fuel emulsions, or as a surfactant for industrial and cosmetic washing and cleaning formulations.

13. ~A fuel, lubricant, fuel additive concentrate, lubricant additive concentrate or water-containing liquid containing one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of claims 1 to 6 and/or a mixture as claimed in any of claims 7 to 9, preferably a water-in-fuel emulsion 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 one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of claims 1 to 6 and/or of a mixture as claimed in any of claims 7 to 9 as an emulsifier.

14. ~A washing or cleaning formulation containing one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of claims 1 to 6 and/or a mixture as claimed in any of claims 7 to 9.

15. ~The emulsion as claimed in claim 13, wherein, in addition to one or more compounds of the formula (Ia) and/or (Ib), one or more further emulsifiers, preferably sorbitan monooleate, C13 oxo alcohol ethoxylates or alkylphenol ethoxylates, and/or one or more biocides, preferably NH4NO3 and/or glyoxal, particularly preferably glyoxal, are present.

16. ~A process for the preparation of an emulsion as claimed in claim 13 or 15, wherein the respective components are mixed with one another and are emulsified in a manner known per se, preferably in a mixing nozzle.