CA2439308A1

CA2439308A1 - Emulsifiers, especially based on polyisobutylenamines

Info

Publication number: CA2439308A1
Application number: CA002439308A
Authority: CA
Inventors: Stephan Hueffer; Cordula Mock-Knoblauch; Gregor Schuermann; Arno Lange
Original assignee: Individual
Current assignee: BASF SE
Priority date: 2001-03-01
Filing date: 2002-02-28
Publication date: 2002-09-12
Also published as: EP1390453A2; MXPA03007384A; AU2002247747A1; WO2002070633A2; DE10109845A1; WO2002070633A3; US20040092412A1; CN1630703A

Abstract

The invention relates to compounds, especially compounds based on polyisobutylenamines, which are suitable for emulsifiers for water-in-oil emulsions. The invention also relates to a method for the production of said compounds and to the use thereof, mainly as additives for fuels and lubricants. The compounds according to the invention are compounds of general formula (I), wherein R1 represents a C1-C8-alkylene or a C2-C8-alkenylene optionally substituted with C1 -C12-alkyl; R2 represents a linear or branched C8-C350-alkyl or a C8-C350-alkenyl; R3 and R4 independently represent H, methyl or ethyl and together do not have more than 2 C atoms; R5 represents H, M+, SO3H, SO3- M+, PO3H, PO3-M+ and C(O)R7, wherein M+ represents NH4+, an alkaline metal ion or 0.5 earth alkaline metal ions; R7 represents one linear C2- to C1O- hydrocarbon radical substituted with at least one hydrophilic group, and y and z independently represent whole numbers from 0 to 50, wherein R5 = H if y = 0 and R6 = H if z = 0.

Description

Emulsifiers, in particular based on polyisobutyleneamines The present invention relates to compounds, in particular based on polyisobutyleneamines, which are suitable as emulsifiers far 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 aqueous liquids, and fuels, lubricants, fuel additive concentrates and lubricant additive concentrates and aqueous liquids containing the novel compounds.
IS
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.
2o For example, US-A 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 polyisobutenyl-substituted succinamide as an emulsifier.
25 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.
3o 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.
BASF AG's German Application filed on January 25, 2000 and having the application 35 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)ro 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 C4 unit; n is either 0 or 1.
BASF AG'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 R~R2NR3 as emulsifiers in water-in-oil emulsions, where R~ is an acyl radical of a mono- or polycarboxylic acid, R1 is derived, inter a.lia, from a poly-1-butylene, poly-2-butylene or isobutylene or a mixture thereof and RZ may be a polyalkylenepolyamine or a polyalkyleneimine radical.
In addition to emulsifiers, friction-reducing additives for fuels and lubricants are also disclosed in the prior art.
Thus, US 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula RI(-O(RZ)-)aNH(CO)-R3-OH, where R1 is C~-to C6o-alkyl, RZ is C~- to C4-alkylene, a is an integer from 1 to 12 and R~ is C~-to C4-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.
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 3o emulsion.
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 a.nd substantially residue-free are required.

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.
We have found that this object is achieved by compounds of the formula I, O R2 Rs Ra \\ ~
/C-N-f-CH-CH-ORS
R ~ ~' ~C-N--~CH-CH-O-~R6 O R2 Rs Ra where R' is unsubstituted or C1-C,2-alkyl-substituted C~-Cg-alkylene or C2-Cg-alkenylene, l0 R2 is linear or branched Cg-C3so-alkyl or C$-C3so-alkenyl, R3 and R4, independently of one another, are each H, methyl or ethyl, and R3 and R4 together have not more than 2 carbon atoms, RS and R6, independently of one another, are each H, M+, S03H, S03 M+, OP03H, OP03~M+ or C(O)RD, M+ is NH4+, an alkali metal ion or 0.5 alkaline earth metal ion, R' is a linear C2-Coo-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 RS isHifyis0,andR6isHifzis0.
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 3o in oil-in-water emulsions, stable vesicles can be produced under the action of ultrasound.

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 Ti02.
The present invention also relates to processes for the preparation of the compounds (1).
These processes are shown schematically in Figure 1.
Fig. 1: Processes for the preparation of compounds (1) where RS = R6 = H.
1o Suitable reaction conditions for the amidation of the dicarboxylic acids with the amines RZ-NHZ (Fig. 1, Reaction step al) to give bisamides (In are known to a person skilled in the art or can be determined by a few preliminary experiments.
The dicarboxylic acids and amines can be reacted with one another bath in organic solvents and in the absence of a solvent. Suitable organic solvents are, for example, Solvesso~ 150 from Shell and isododecane.
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 2o continuously during the reaction. Purification of the resulting bisamides (II) - before further reaction - is generally unnecessary.
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 RS and R6 are each H (Fig. 1, Reaction step a2). This reaction is carned out in general in the presence of a conventional basic catalyst, such as KOH, NaOH, NaOMe, KtBuO, Ca(OH)2 or CaO, or a support catalyst, such as a zeolite.
Hydrophilic groups can be introduced into the novel compounds (I) thus obtainable, in 3o which RS and R6 are each H. For example, the novel compounds (I) in which RS and R6 are each H can be sulfated with S03 to give sulfuric esters ((n where RS = R6 =
S03H) reacted with P40~o to give phosphoric esters ((I) where R5 = R6 = OP03H) or reacted with compounds H02C-R' to give esters ((I) where RS = R6 = C(O)R'), 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 October 19, 1999 and in the PCT
Application with the application number PCT/EP/00/09923.
By adding NH3 or suitable alkali (alkaline earth) metal salts, such as alkali (alkaline earth) metal hydroxides, the corresponding sulfates (I) where Rs = R6 = 503, or phosphates (I) where RS = R6 = OP03M+, where M+ is NH4+, an alkali metal ion or 0.5 alkaline earth metal ion, can be prepared from the sulfuric esters and phosphoric esters, respectively.
Alternatively (Fig. 1, Reaction steps b1, b2 and b3), compounds (I) in which Rs and R6 are to each H can be prepared by first reacting amines RZ-NH2 with alkylene oxides (III) to give alcohols of the formula IV. Dicarboxylic acids HOZC-R1-C02H are then reacted with the alcohols (IV), in general under the same reaction conditions which are applied to the reaction of the dicarboxylic acids HOZC-R1-C02H with the amines RZ-NH2. The resulting bisamides of the formula V where Rs = R6 = H can be reacted with alkylene oxides III to give compounds (I) in which Rs and R6 are each H. Hydrophilic groups can be introduced into the bisamides of the formula V where R5 = R6 = H also directly, as described in the preceding section.
Dicarboxylic acids HOZC-R1-C02H in which R1 is C1-C8-alkylene or C2-Cg-alkenylene and is unsubstituted or substituted by C~-C12-alkyl are used. In the present invention, the term alkenylene also includes polyunsaturated bivalent hydrocarbon radicals R1.
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 Ci-C12-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.
In general, amines R2-NH2 in which R2 is linear or branched C$-C3so-alkyl or C8-C3so 3o alkenyl are suitable for the preparation of compounds (I) in which Rs and R6 are each H.
Here, alkenyl also includes polyunsaturated hydrocarbon radicals R2.
Amines R2-NHz in which RZ is C22-C3so-polyisobutenyl are preferably used.
Polyisobutyleneamines R2-NHz where RZ is C22-C3so-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.
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 to context of the present invention, this is understood as meaning an amount of >_ 70, preferably >_ 80, particularly preferably > 85, mol % of vinylidene groups.
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.
2o 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 <_ 2.5, preferably <_ 2Ø Polydispersity is understood as meaning the quotient MW/Mn of weight average molecular weight MW and number average molecular weight Mn. The polydispersity is a measure of the molecular weight distribution of a polymer.
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~ from BASF AG, such as 3o Glissopal~ 1000 having an M" of 1000, Glissopal~ V 33 having an M~ of 550 and Glissopal~ 2300 having an M" of 2300.
Examples of commercially available polyisobutyleneamines are the compounds obtainable under the trade name Kerocom~ PIBA from BASF AG.

Examples of suitable alkylene oxides (Ill) are ethylene oxide, propylene oxide, 1-butylene oxide and 2-butylene oxide. Ethylene oxide and propylene oxide are preferably used.
Compounds in which R' is a linear CZ-Clo-hydrocarbon radical substituted by at least one hydrophilic group are used for R'-COZH. The term CZ-Coo-hydrocarbon radical includes C2-Coo-alkyl, C2-Clo-alkenyl and C~-Clo-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 -NH2, -NH3+, -NR3+ where R is C,-C6-alkyl, -C02H, -C02 , OP03H and 1o OP03-. Compounds where R' corresponds to the formula VI where n = 1 to 4 are preferably used for R~-C02H. R'-COZH 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.

~CH2~
'~ C02 is (VI) 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.
The novel compounds (n 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.
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.
3o 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 RS and R6 are each H are preferably used. Such water-in-oil emlusions are used, for example, in the cosmetics or pharmaceutical sector.

_ g _ 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 linoleruc acid.
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 lr~ating oil. Compounds of the formula I in which RS
and R6 are not H are preferably used, and compounds of the formula I in which RS and R6 are each S03H, S03 M~ or C(O)RD are particularly preferably used. All conventional fuels may be used, for example diesel fuels, gasoline fuel and kerosene. Diesel fuel is preferably used.
Novel water-in-fuel emulsions may also contain one or more C1-C4-alcohols and/or monoethylene glycol, in particular monoethylene glycol. The amount of C~-C4-alcohol and/or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water. By adding one or more C1-C4-alcohols and/or monoethylene glycol, for example, the temperature range in which the emulsion is stable can be broadened.
The novel water-in-fuel emulsions have high stability and good efficiency during 2o combustion. It is also possible to obtain good exhaust gas values, the emission of soot and NOR 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.
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, C13-oxo alcohol ethoxylates and alkylphenol ethoxylates, and the block copolymers of ethylene oxide and propylene oxide, such as the Pluronic~
grades from BASF AG. Sorbitan monooleate, CI3-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 emulsifiers 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, °Io 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°lo by weight stated for the novel emulsifier alone.
l0 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 December 8, 1998, was used.
Water-in-oil emulsions for the cosmetics sector can be prepared in the same way as water-in-fuel emulsions.
In addition to their surfactant and emulsifying properties, the novel compounds (I) also 2o have a lubricity-improving and corrosion-inhibiting effect. Moreover, they improve the antiwear behavior of liquids. The novel compounds (1) 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.
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.
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.

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.
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.
Novel fuel additive concentrates and lubricant additive concentrates contain -in addition to 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.
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 July 28, 2000 (page 14 et seq.), in BASF AG's German Application, application number 100 03 105.6, of January 25, 2000, and in BASF
AG's PCT Application having the application number PCT/EP/O1/00496. 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.
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.
Further conventional components are, for example, further corrosion-inhibiting additives, 3o 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.

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.
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 or methylcyclopentadienyl-t0 manganesetricarbonyl.
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.
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 2o lubricants themselves and Garner oils.
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) (alkylphenol-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 those based on polyisobutylene and on poly-a-olefins, having a number average molecular weight of from 400 to 1800. Polyethylene oxides, 3o 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 aqueous liquids contain the novel compounds (~, 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 t o Example 1: Preparation of the compounds of the formula I
The composition of the compounds prepared is shown in table 1. The polyisobutylene-amine used was Kerocom~ PIBA from BASF AG.
Synthesis of the comounds A1, A2, A3 and A4 28 g of adipic acid were added to 750 g of polyisobutyleneamine (M~ = 1000, amine number = 36) and heated for 3 hours at 200°C under reduced pressure.
When water no longer distilled off, the product A1 thus obtained was cooled and filled.
A4 was prepared analogously by reacting polyisobutyleneamine (Mn = 550, amine number = 36) with adipic acid.
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.
/C N2 H /C N-~-fCH2~0-~H
\2)4 R ( \2)4 R
C N-H C N-~-fCH2~0--~H
O R2 ~ R2 A1 Bl (where R2= Polyisobutylenyl) Synthesis of compound B 1 282 g (about 130 mmol) of compound A1 and 3.95 g (35.2 mmol) of KtBuO were combined and volatile components were removed in a rotary evaporator at 100°C and 3 mbar. The reaction mixture was initially taken in a 2 1 metal reactor and then blanketed three times with 5 bar nitrogen each time. The reactor contents were heated to 120°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 B 1 having a 1o polyethylene glycol moiety of 5.2% was obtained.
Synthesis of compounds C1, C2 and C3 Compounds B l, B2 and B3 were sulfated in a continuous process using an S03/air mixture having an S03 content of 7% by volume. The reaction was carried out at 65°C in a vertical falling-film reactor having a length of 95 cm and an internal diameter of 5 cm. About 400 glli of compound B l, B2 or B3 as an 80% strength by weight solution in a suitable hydrocarbon, such as isododecane, heptane or nuhagol, were metered into the reactor from above. The amount of S03/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°C with 25% strength by weight aqueous NaOH solution.

O
\C N CH2~0 SO-3M+
I
( \2)4 R
C N-f --ECH2~p-~Sp-3M+
R
O

Synthesis of D1 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°C to 180°C for 90 minutes under reduced pressure.

/C N~CH2~0 ~C--f CH2-~ NCO -(CH2)4 R O 2 N-~-~CH2~O -~.Z C--~CH2~CH+
~C02 Synthesis of DZ
The reaction of compound B 1 with 45 g of L-aspartic acid to give product DZ
was carried out analogously to the synthesis of D 1.

Table 1. Composition of the novel compounds Batch M" Of R1 y + z R'-COZH RS =
Rz_~Z (R3, R4 (amino acid) R6 H; ethylene oxide) A 1 1000 (CHz)4 H

A2 1000 (CHZ)3 H

A3 1000 (CH2)z H

A4 550 (CHZ)4 . H

B 1 1000 (CH2)4 15 H

B2 1000 (CHZ)2 10 H

B3 550 (CH~)4 10 H

C 1 1000 (CH2)4 15 S03~VI+

C2 1000 (CH2)2 10 503+

C3 550 (CH2)4 10 503+

D1 1000 (CH2)4 15 L- lutamic C(O)R' acid D2 1000 (CH2)4 15 L-as artic C(O)R' acid D3 550 (CH2)a 10 L- lutamic C(O)R' acid Example 2: Water-in-fuel emulsions In each case a 1 °1o 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 (C 1, C2, C3, D1, D2 or D3) and 2 parts of a C13-oxo alcohol ethoxylate (Lutensol~
TO 7 from to BASF AG), and 2 parts of an alkylphenol ethoxylate (Emulan~ 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~ (Jahnke and Kunkel laboratory apparatus T25).
For comparison, 6 parts of sorbitan monooleate (S-MAZ 80 from BASF AG) were used instead of the novel compounds.

Table 2 Batch Emulsifier Amount of Time to Corrosion emulsifier beginning of protection in the phase mixture se aration 1 C 1 I % 26 d +0 2 C2 I% 28 d +0 3 C3 1 % 30 d +0 4 Dl I% >30d ++

D2 1 % . > 30 d ++

6 D3 1 % 29 d ++

Com . S-MAZ 80 1 % 6 h -0 Com . S-MAZ 80 2% 19 d -0 The results in table 2 show that the water-in-fuel emulsions of the novel compounds show 5 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 A 20 x 40 mm iron sheet is blasted with 40 ~m glass beads and then -analogously to ASTM D-665 - immersed in the emulsions prepared under Example l and stored for hours at 40 ~ 1 °C. After 24 hours, the iron sheet is investigated for rust formation. Here, the meanings are as follows:
++ 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.
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°l0 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 The novel compounds B3, C1, D1 and D2 were each dissolved individually in an additive-free 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 to 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.
Table 3 Additive Length of the furrows [gym]
-., - -- 595 No additives Com ound B3 440 Com ound C 1 370 Com ound D1 365 Com ound D2 390 C16- to C22-carboxylic acid mixture 420 (PC30~ from Elfj For comparison, the furrow formation with the use of additive-free diesel fuel and with the use of diesel fuel to which C16- to C2z-carboxylic acid mixture has been added was observed.

Claims

We claim:-

1. A compound of the formula I
where R1 is unsubstituted or C1-C12-alkyl-substituted C1-C8-alkylene or C2-C8-alkenylene, preferably unsubstituted C2-C4-alkylene, R2 is linear or branched C8-C350-alkyl or C8-C350-alkenyl, preferably C22-C350-polyisobutenyl, R3 and R4, independently of one another, are each H, methyl or ethyl and together have not more than 2 carbon atoms, R5 and R6, independently of one another, are each H, M+, SO3H, SO3-M+, OPO3H, OPO3-M+ or C(O)R7, M+ is NH4+, an alkali metal ion or 0.5 alkaline earth metal ion, R7 is a linear C2-C10-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 R5 is H if y is 0, and R6 is H if z is 0.

2. A compound as claimed in claim 1, wherein R2 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 R5 and R6 are each C(O)R7, wherein R7 corresponds to the formula VI
where 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 HO2C-R1-CO2H with amines R2-NH2 and alkylene oxides of the formula III in a suitable sequence, and, if required, by reacting the compound obtained in this manner with SO3, or compounds R7C(O)OH
and, if required, then with NH3 or alkali metal (alkaline earth metal) salts.

5. A compound of the formula II
where R1 is unsubstituted or C1-C12-alkyl-substituted C1-C8-alkylene or C2- to alkenylene, and R2 is linear or branched C8-C350-alkyl or C8-C350-alkenyl.

6. A compound of the formula IV
where R2 is linear or branched C8-C350-alkyl or C8-C350-alkenyl, R3 and R4, independently of one another, are each H, methyl or ethyl and together contain not more than 2 carbon atoms, and R5 is H, M+, SO3H, SO3-M+, OPO3H, OPO3-M+ or C(O)R7, M+ is NH4+, an alkali metal ion or 0.5 alkaline earth metal ion and R7 is a linear C2-C10-hydrocarbon radical substituted by at least one hydrophilic group.

7. A compound of the formula V
where R1 is unsubstituted C1-C12-alkyl-substituted C1-C8-alkylene or C2-C8-alkenylene, R2 is linear or branched C8-C350-alkyl or C8-C350-alkenyl, R3 and R4, independently of one another, are each H, methyl or ethyl and together contain not more than 2 carbon atoms, R5 and R6, independently of one another, are each H, M+, SO3H, SO3-M+, OPO3H, OPO3-M+ or C(O)R7, M+ is NH4+, an alkali metal ion or 0.5 alkaline earth metal ion, and R7 is a linear C2-C10-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 R5 and R6 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 R5 and R6 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 R5 and R6 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, C13-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.