WO2002070633A2

WO2002070633A2 - Emulsifiers, especially based on polyisobutylenamines

Info

Publication number: WO2002070633A2
Application number: PCT/EP2002/002197
Authority: WO
Inventors: Stephan Hüffer; Cordula Mock-Knoblauch; Gregor Schürmann; Arno Lange
Original assignee: Basf Aktiengesellschaft
Priority date: 2001-03-01
Filing date: 2002-02-28
Publication date: 2002-09-12
Also published as: CN1630703A; CA2439308A1; US20040092412A1; AU2002247747A1; EP1390453A2; MXPA03007384A; DE10109845A1; WO2002070633A3

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 C¿1?-C8-alkylene or a C2-C8-alkenylene optionally substituted with C1 -C12-alkyl; R?2¿ represents a linear or branched C¿8?-C350-alkyl or a C8-C350-alkenyl; R?3 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+, PO¿3H, PO3-M+ and ¿C(O)R7, wherein M+ represents NH¿4?+, an alkaline metal ion or 0.5 earth alkaline metal ions; R7 represents one linear C¿2?- to C1O- hydrocarbon radical substituted with at least one hydrophilic group, and y and z independently represent whole numbers from 0 to 50, wherein R?5¿ = H if y = 0 and R6 = H if z = 0.

Description

Emulsifiers, in particular based on polyisobutylene amines

The present invention relates to compounds, in particular based on polyisobutylene amines, which are suitable as emulsifiers for water-in-oil emulsions, to processes for the preparation of such compounds and to the emulsions themselves.

The invention also relates to the use of such compounds as additives for fuels and lubricants, and as a corrosion-inhibiting additive in aqueous liquids, as well as fuels, lubricants, fuel and lubricant additive concentrates and aqueous liquids containing the compounds according to the invention.

Compounds of various types with emulsifying properties are known from the prior art. Among others, derivatives of succinic anhydride substituted with a polyisobutenyl group are used in various applications.

For example, US Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and a succinic anhydride substituted with a polyisobutenyl group, an (earth) alkali metal salt of a succinic acid substituted with a polyisobutenyl group or a succinic acid amide substituted with a polyisobutenyl group as Emulsifier included.

GB-A 2,157,744 discloses drilling fluids which contain both an emulsifier, namely graft or block copolymers of polycarboxylic acids and polyethylene glycol, and surfactants. Compounds which are prepared from a succinic anhydride substituted with a polyisobutenyl group and polyols, polyamines, hydroxycarboxylic acids or amino alcohols are used as surfactants. EP-A 0 156 572 describes the use of anionic surface-active substances based on succinic acid derivatives substituted with polyisobutenyl groups for the production of water-in-oil or oil-in-water emulsions.

The German application filed by BASF AG on January 25, 2000 with the file number 100 03 105.6 describes the use of alkoxylated polyisobutylenes (polyisobutenes) as emulsifiers in water-in-fuel emulsions. These alkoxylated polyisobutylenes can be described by the general formula R- (CH ₂ ) _n _ (OA) _m -OH. R is a polyisobutylene with a weight average molecular weight of 300 to 2300, preferably 500 to 2000. A is an alkylene radical with 2 to 8 carbon atoms. The number m is a number from 1 to 200, which is chosen so that the alkoxylated polyisobutylene contains 0.2 to 1.5 alkylene oxide units per C ₄ unit, preferably 0.5 alkylene oxide units per C unit; n is either 0 or 1.

The German application filed by BASF AG on July 28, 2000 with the file number 100 36 956.1 describes, among other things, the use of amides of the general formula R ^! R ² NR ³ as emulsifiers in water-in-oil emulsions, where R ^{3 represents} an acyl radical of a mono- or polycarboxylic acid, and R ¹ includes a poly-1-butylene, -2-butylene or wo-butylene or mixtures derived therefrom and R can be a polyalkylenepolyamine or a polyalkylenimine radical.

Friction reducing additives for fuels and lubricants as well as emulsifiers are already known from the prior art.

No. 5,858,029 describes friction-reducing additives for fuels and lubricants, compounds of the formula R ¹ (-O (R ² ) -) _a NH (CO) -R ³ - OH being used in particular as friction-reducing additives, wherein R ^{1 is} for a - to C ₆₀ - alkyl radical, R is a Ci to C ₄ alkylene radical, a is an integer from 1 to 12 and R is Ci to C ₄ alkylene or substituted alkylene or cycloalkylene. Succinimides substituted with polyisobutenyl groups may also be present as dispersants and polyalkylene amines such as polyisobutylene amines may be present as surfactants.

The above-mentioned compounds known from the prior art have various disadvantages with regard to production and / or product properties. Some compounds fall in different yields during synthesis

By-products, which - if not removed - discontinue one constant viscosity of the emulsifier can complicate. Disadvantages can also arise in the production of emulsions: the emulsions often have insufficient stability, so that phase separation occurs during storage. The emulsifiers used must therefore be used in high concentrations to enable 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 disadvantages mentioned. Especially in the field of water-in-fuel emulsions, emulsifiers are needed that produce relatively stable emulsions and also enable the most complete and largely residue-free combustion of the fuel.

The object of the present invention is to provide further compounds which can be used as emulsifiers in oil-in-water and water-in-oil emulsions.

The above object is achieved by compounds of the general formula I

(I)

where R ¹ for an optionally with C _! -C ₁₂ alkyl substituted Cj-Cg-alkylene or C ₂ - Cg-alkenylene,

R ² denotes a linear or branched C ₈ -C ₃₅₀ alkyl or C ₈ -C ₃₅₀ alkenyl,

R ³ and R ^{4 are} independently H, methyl or ethyl, and R ³ and R ⁴ together have no more than 2 C atoms, R ⁵ and R ⁶ independently of one another are H, M ^{1 "} , SO ₃ H, SO M *, PO ₃ H, PO ₃ ^" M ^, and also C (O) R ⁷ ,

where M stands for NEW ^"" , an alkali metal ion or 0.5 alkaline earth metal ions,

R ^{7 is} a linear C ₂ -C ₁₀ hydrocarbon radical substituted with at least one hydrophilic group, and

y and z are independently integers from 0 to 50,

where R ⁵ = H if y = 0 and R ⁶ = H if z = 0.

The inventive compounds (I) can be used as emulsifiers in water-in-oil emulsions. The advantage here is that often lower concentrations are required to produce stable emulsions than when using conventional emulsifiers. If the compounds according to the invention are used in oil-in-water emulsions, stable nesicles can be produced under the action of ultrasound. The Nerbindungen invention are also applicable in many ways, for. B. as additives in fuels and lubricants, as a corrosion-inhibiting additive in aqueous liquids and as dispersants for pigments such as TiO ₂ .

The present invention also relates to processes for the preparation of the compounds (I). These processes are shown schematically in FIG. 1.

Fig. 1: Process for the preparation of compounds (I) with R 5 = = ₀ R6 _^ = - H.

Suitable reaction conditions for the amidation of the dicarboxylic acids HO ₂ CR ^I -CO ₂ H with the amines R ² -ΝH ₂ (FIG. 1, reaction step a1) to give bisamides (II) are known to the person skilled in the art or can be determined in the course of a few preliminary tests.

The dicarboxylic acids and amines can be reacted with one another both in an organic solvent and in bulk. 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 5 to 50 mbar, and the water formed is distilled off continuously during the reaction. It is generally not necessary to purify the bisamides (II) formed before further reaction.

The bisamide (II) thus obtainable is then reacted with alkylene oxides (III) using processes known to those skilled in the art to give alcohols of the general formula I in which R = R = H (FIG. 1, reaction step a2). This reaction is generally carried out in the presence of a customary basic catalyst such as KOH, NaOH, NaOMe, K / BuO, Ca (OH) ₂ , CaO or supported catalysts such as zeolites.

Hydrophilic groups can be introduced into the thus obtainable compounds (I) in which R ⁵ = R ⁶ = H. For example, the compounds (I) according to the invention in which R ⁵ = R ⁶ = H can be prepared by standard methods - as described, for example, in Falbe (editor), Surfactants in consumer products 1986, Springer Verlag Berlin, p. 54 ff., In the US application with the file number 60 160 212 dated October 19, 1999 and the PCT application with the file number PCT / EP / 00/09923 - sulfated with SO ₃ to sulfuric acid esters ((I) with R ⁵ = R ⁶ = SO ₃ H) , with P ₄ O ₁₀ to form phosphoric acid esters ((I) with R = R = PO ₃ H) or with compounds HO ₂ CR to form esters ((I) with R ⁵ = R ⁶ = C (O) R ⁷ ) become.

By adding NH ₃ or suitable (earth) alkali metal salts such as (earth) alkali metal hydroxides, the corresponding sulfates, (I) with R ⁵ = R ⁶ = SOsTVf ^{1 "} , or phosphates, (I ) with R ⁵ = R ⁶ = PO ₃ ^ M ⁺ , where M ^{+ stands} for NH ₄ ⁺ , an alkali metal ion or 0.5 alkaline earth metal ions.

Alternatively (FIG. 1, reaction steps b1, b2 and b3), compounds (I) in which R ⁵ = R ⁶ = H can be prepared by first amines R ² -NH ₂ with alkylene oxides (III) to give the alcohols general formula IV implements. Dicarboxylic acids HO ₂ CR ¹ -CO ₂ H are then reacted with the alcohols (IV), generally under the same reaction conditions which are applied in the reaction of the dicarboxylic acids HO ₂ CR ¹ -CO ₂ H with the amines R ² -NH ₂ . The bisamides of the general formula V thus obtained with R ⁵ = R ⁶ = H can be reacted with alkylene oxides III to give compounds (I) in which R ⁵ = R ⁶ = H. In the bisamides of the general formula V with R ⁵ = R ⁶ = H can hydrophilic groups can also be introduced directly, as described in the previous section.

Dicarboxylic acids HO ₂ CR ^! -CO ₂ H used, in which R ^{1 is} a Ct-Cs-alkylene or C ₂ -C ₈ -alkenylene and is optionally substituted with -C-C ₂ alkyl groups. The term "alkenylene" in the present invention also includes polyunsaturated bivalent hydrocarbon radicals R ¹ .

Suitable dicarboxylic acids are, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, which can optionally carry C 1 -C 4 -alkyl groups. The use of unsubstituted dicarboxylic acids is preferred. Of these, succinic acid, glutaric acid, adipic acid, pimelic acid or suberic acid are preferably used, particularly preferably succinic acid, glutaric acid or adipic acid.

9

In general, amines R -NH ₂ , in which R is a linear or branched C ₈ -C ₃₅ o -alkyl or C ₈ -C ₃ 5 ₀ -alkenyl, are used to prepare compounds (I) in which R ⁵ = R ⁶ = H is suitable. "Alkenyl" also includes polyunsaturated hydrocarbon radicals R ² .

9 9

Amines R -NH ₂ are preferably used in which R represents a C ₂ -C ₃₅ o-polyisobutenyl.

9 9

Polyisobutylene amines R -NH ₂ with R = C ₂₂ -C ₃₅ o-polyisobutenyl are converted from the corresponding polyisobutylenes by standard methods, as described, for example, in DE-A 196 20 262, EP-A 0 244 616 and WO-A 97/03946 are described. The amount of amino groups can be determined by titration with HC1 and then converted into mg KOH per g substance. The proportion of amino groups per unit weight of substance is then the amine number. In general, polyisobutylenes which have a number average molecular weight of 300 to 5000, preferably from 500 to 2300, particularly preferably from 500 to 1000, are used for the preparation of the polyisobutylene amines.

Of the polyisobutylenes with a number-average molecular weight in the ranges mentioned, preference is given to those which have a high content of vinylidene groups. In the context of the present invention, this means a Proportion of vinylidene groups of> 70 mol%, preferably a proportion of vinylidene groups of> 80 mol%, particularly preferably a proportion of vinylidene groups of> 85 mol%.

Those polyisobutylenes which have a number-average molecular weight in the abovementioned ranges, a high content of vinylidene groups and a uniform polymer structure are particularly preferably used. Examples of polyisobutylenes with a uniform polymer structure are those polyisobutylenes which are composed of at least 85% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of isobutylene units.

Polyisobutylenes with a number average molecular weight in the ranges mentioned, a high content of vinylidene groups and a uniform framework structure can furthermore have a polydispersity of <2.5, preferably of <2.0. Polydispersity means the quotient M _w / M _n from the weight-average molecular weight M _w and the number-average molecular weight M _n . Polydispersity is a measure of the molecular weight distribution of a polymer.

Polyisobutylenes with a number average molecular weight in the ranges mentioned, which are essentially composed 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 with an M _n of 1000, Glissopal ® V 33 with an M _n of 550 and Glissopal® 2300 with an M "of 2300.

Examples of commercially available polyisobutylene amines are the compounds available from BASF AG under the trade name Kerocom® PIB A.

Examples of suitable alkylene oxides (III) are ethylene oxide, propylene oxide, 1-butylene oxide and 2-butylene oxide. Ethylene oxide and propylene oxide are preferably used.

7 7 For R -CO ₂ H, compounds are used in which R is a linear C ₂ -C hydrocarbon radical substituted with at least one hydrophilic group. By the term "C ₂ -C ₁ o-hydrocarbon radical" C -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl and C ₇ -C _10, - alkylaryl comprises. The term "hydrophilic groups" also includes positively or negatively charged groups, the term "alkenyl" both mono- and polyunsaturated hydrocarbon radicals. Examples of hydrophilic groups are -NH ₂ , -NH ₃ ⁺ , -NR ₃ ⁺ with R = Ci-Cβ-alkyl, -CO ₂ H, -CO ₂ ^" , -OPO ₃ H, and -OPO ₃ ^~ . Preferred for R ⁷ -CO ₂ H n

Compounds used, wherein R corresponds to the general formula VI with n = 1 to 4. R ⁷ -CO ₂ H corresponds, for example, to amino acids with at least one additional carboxyl group in the molecule. The use of aspartic acid (n = 1) and glutamic acid (n = 2) is particularly preferred.

(VI)

In addition to L-amino acids, the corresponding D-amino acids or mixtures such as the racemates of the D- and L-amino acids can also be used.

The compounds (I) according to the invention can be used as emulsifiers in the preparation of water-in-oil emulsions. This use is also the subject of the invention. Purification of these compounds and their intermediates may be necessary, for example when these compounds are used as emulsifiers for water-in-oil emulsions in the cosmetics or pharmaceutical sector.

The water-in-oil emulsions according to the invention generally contain 95 to 60% by weight of oil, 3 to 35% by weight of water and 0.2 to 10% by weight of a compound of the general formula I according to the invention.

Compounds according to the invention of the general formula I are used for water-in-oil emulsions in which the oil phase is formed from a vegetable, animal or synthetic oil or fat. Compounds of the general formula I in which R ⁵ = R ⁶ = H are preferably used. Such water-in-oil emulsions are used, for example, in the cosmetics or pharmaceutical field.

Examples of vegetable, animal or synthetic oils or fats are triglycerides and glycol esters (esters of glycolic acid) of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.

Compounds of the general formula I are also used in water-in-oil emulsions in which the oil phase consists of a fuel, light or heavy heating oil is formed. Compounds of the general formula I are preferably used, in which R ⁵ , R ⁶ ≠ H, compounds of the general formula I in which R ⁵ = R ⁶ = SO ₃ H, SO ₃ ^~ M ⁺ or C ( O) R ⁷ . All common types of fuel can be used, for example diesel fuel, petrol and kerosene. Diesel fuel is preferably used.

Water-in-fuel emulsions according to the invention can also contain one or more Ci-C ₄ alcohols and / or monoethylene glycol, in particular monoefhylene glycol. The amount of Cr alcohol and / or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water. By adding one or more C 1 -C ₄ alcohols and / or monoethylene glycol, for example, the temperature range in which the emulsion is stable can be broadened.

The water-in-fuel emulsions according to the invention have high stability and good combustion efficiency. Good exhaust gas values can still be obtained, the emission of soot and NO _{x being} significantly reduced, particularly in the case of diesel engines. A largely complete and residue-free combustion can be achieved without deposits on the assemblies of the combustion apparatus, for example injection nozzles, pistons, annular grooves, valves and cylinder head.

The water-in-fuel emulsions according to the present invention can have further components in addition to the components mentioned above. These are, for example, further emulsifiers such as sodium lauryl sulfate, quaternary ammonium salts such as ammonium nitrate, alkyl glycosides, lecithins, polyethylene glycol ethers and esters, sorbitan oleates, stearates and ricinolates, C ₁₃ oxo alcohol ethoxylates and alkyl phenol ethoxylates and ethylene oxide copolymers and the ethylene oxide copolymers from and block copolymers from ® types from BASF AG. Sorbitan monooleate, C ₁₃ 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 above-mentioned further emulsifiers together with the emulsifiers according to the invention is preferably used for the water-in-fuel emulsions according to the invention. If these further emulsifiers are used, this is done in amounts of 0.5 to 5% by weight, preferably 1 to 2.5% by weight, based on the overall composition. The amount of this further emulsifier is chosen so that the total amount of emulsifier, that is to say the emulsifier according to the invention plus further emulsifier, does not exceed the amount of 0.2 to 10% by weight stated for the emulsifier according to the invention alone.

To produce the water-in-oil emulsions according to the invention, the selected emulsifier according to the invention is mixed with the oil, the water and the other components which can be used optionally and emulsified in a manner known per se. For example, the emulsification can be carried out in a rotor mixer, by means of a mixing nozzle or by an ultrasound probe. Particularly good results were achieved if a mixing nozzle of the type used as disclosed in the German application, file number: 198 56 604 from BASF AG on December 8, 1998 was used. Water-in-oil emulsions for the cosmetics sector can be produced as well as water-in-fuel emulsions.

In addition to their surface-active and emulsifying properties, the compounds (I) according to the invention also have a lubricity-improving and corrosion-inhibiting action. They also improve the wear protection behavior of liquids. The compounds (I) according to the invention are therefore used as additives for lubricants, fuels and aqueous liquids such as coolant liquids or drilling and cutting liquids. This use is also the subject of the present invention.

The compounds (I) according to the invention can be added directly to the fuels and lubricants — together with other components. Alternatively, the compounds (I) according to the invention can first be mixed with other components to give fuel or lubricant additive concentrates. These fuel or lubricant additive concentrates according to the invention can be added to the fuels or lubricants undiluted or diluted with one or more solvents or carrier oils. The addition in dilute form is preferred.

The fuels, lubricants, fuel additive and lubricant additive concentrates, and aqueous liquids, which the compounds of the invention of the general Formula I contain are also the subject of the present invention and will be explained in more detail below.

Fuels according to the invention generally contain - in addition to conventional components - at least one compound according to the invention of the general formula I in an amount of 10 to 5000 ppm, preferably in an amount of 20 to 2000 ppm, based on the total amount.

Lubricants according to the invention generally contain between 90 and 99.9% by weight, preferably between 95 and 99.5% by weight, of a liquid, semi-solid or solid lubricant and between 0.1 and 10% by weight, preferably between 0 , 5 and 5 wt .-% of a compound (I) according to the invention, based on the total amount.

Fuel additive and lubricant additive concentrates according to the invention contain - in addition to conventional components - at least one compound according to the invention of the general formula I in proportions of 0.1 to 80% by weight, in particular 0.5 to 60% by weight, based on the total weight of the concentrate.

Typical components for fuels or fuel additive concentrates are, for example, additives with detergent action, as described in the German application by BASF AG, file number 100 36 956.1, dated July 28, 2000 (page 14 ff), in the German application by BASF AG, file number 100 03 105.6, dated January 25, 2000 and in the PCT application of BASF AG with the file number PCT / EP / 01/00496. The additives mentioned there and other fuel additives with polar groupings described there are also part of the present application and are included by reference.

The fuels and fuel additive concentrates according to the invention can 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, 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, 196 14 349, and WO-A 96/03479. Other common components are, for example, other corrosion-inhibiting additives, antioxidants, stabilizers, antistatic agents, organometallic compounds, wear protection additives, dyes and cetane number improvers, flow improvers, biocides such as glutardialdehyde or glyoxal. The biocides are usually used in an amount of 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 tend to form films, or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection.

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 methylcyclopentadienylmanganese tricarbonyl.

Examples of cetane number improvers are organic C ₂ -C ₁₀ nitrates such as 2-ethylhexyl nitrate, and inorganic cetane number improvers for the aqueous phase such as ammonium nitrate. 2-Ethylhexyl nitrate and ammonium nitrate are preferably used. The cetane number improvers are usually used in an amount of 0.05 to 5% by weight, based on the total weight of the concentrate.

Suitable solvents for the fuel and lubricant additive concentrates according to the invention are aliphatic and aromatic hydrocarbons such as solvent naphtha, isododecane, mihagol, the fuels and lubricants themselves and carrier oils.

Carrier oils, which also serve to dilute the fuel 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", as well as synthetic carrier oils based on polyolefins, (poly) esters, ( Alkylphenol-started) polyethers, (aliphatic) (alkylphenol-started) 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 poly-α-olefins, with a number average molecular weight from 400 to 1800. Polyethylene oxides, polypropylene oxides, polybutene oxides and mixtures thereof are also suitable carrier oils. Further suitable carrier oils and carrier oil mixtures are described, for example, in the documents 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.

Aqueous liquids according to the invention contain the compounds (I) according to the invention optionally in combination with other customary corrosion-inhibiting additives, generally in a proportion of about 1 to 10% by weight, based on the total amount.

The invention will now be explained in more detail in the following examples.

embodiments

Example 1: Preparation of the compounds of general formula I.

The composition of the compounds prepared can be found in Table 1. Kerocom® PIB A from BASF AG was used as the polyisobutylene amine.

Synthesis of the compounds AI, A2, A3, and A4

750 g of polyisobutylene amine (M _n = 1000, amine number = 36) were mixed with 28 g of adipic acid and heated at 200 ° C. under vacuum for 3 hours. After water no longer distilled off, the product obtained in this way was cooled and bottled.

A4 was prepared analogously by reacting polyisobutylene amine (M "= 550, amine number = 36) with adipic acid.

The reaction of polyisobutylene amine (M = 1000, amine number = 36) with the homologous dicarboxylic acids succinic acid (product A3) and glutaric acid (product A2) was carried out analogously.

AI Bl

(with R ² = polyisobutylenyl)

Synthesis of compound Bl

282 g (approx. 130 mmol) of compound AI and 3.95 g (35.2 mmol) of KtBuO were combined and volatile constituents were removed on a rotary evaporator at 100 ° C. and 3 mbar. The reaction mixture was placed in a 2 1 metal reactor and then rendered inert 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. The mixture was stirred until the pressure was constant. After the reactor had been cooled and let down, Compound B1 with a 5.2% polyefhylene glycol content was obtained.

Synthesis of the compounds CI, C2, C3

The compounds B1, B2 and B3 were sulfated in a continuous process using an SO ₃ / air mixture with an SO ₃ content of 7% by volume. The reaction was carried out at 65 ° C in a vertical falling film reactor with a length of 95 cm and an inner diameter of 5 cm. About 400 g / h of the compounds B1, B2 or B3 were metered into the reactor as an 80% by weight solution in a suitable hydrocarbon such as isododecane, heptane or mihagol. The amount of the SO ₃ -air mixture fed to the falling film reactor was regulated via the acid number of the sulfated product. The acid number is a measure of the proportion of acid groups, it is determined by titration with KOH and given in mg KOH per g substance. The acid numbers were 22 for CI, 26 for C2 and 41 for C3. The products were neutralized discontinuously at 25 ° C. with 25% by weight aqueous ΝaOH solution.

CI

Synthesis of Dl

500 g of the compound B1 were dissolved in 500 ml of Mihagol, 48 g of L-glutamic acid were added and the mixture was heated at 160 ° C. to 180 ° C. for 90 minutes under vacuum.

dl

Synthesis of D2

Analogously to the synthesis of Dl, the compound B1 was reacted with 45 g of L-aspartic acid to give product D2.

Table 1. Composition of the compounds according to the invention

Example 2: Water-in-fuel emulsions

In each case, a 1% by weight solution of an emulsifier mixture in diesel fuel was prepared, which consists of 6 parts from a compound according to the invention (CI, C2, C3, Dl, D2, or D3) and 2 parts of a C ₃ -oxoalcohol ethoxylate (Lutensol® TO 7 from BASF-AG) and composed of 2 parts from an alkylphenol ethoxylate (Emulan® OP 25). With an Ultra-Turrax® (Jahnke and Kunkel laboratory device T25), 500 g of this mixture were stirred with 100 ml of water for 15 minutes at a speed of 24000 / min.

For comparison, 6 parts of sorbitan monooleate (S-MAZ 80 from BASF-AG) were used instead of the compounds according to the invention. Table 2

It can be seen from the results in Table 2 that the water-in-fuel emulsions of the compounds according to the invention show hardly any signs of phase separation after 30 days of storage, whereas phase separation was observed after 6 hours in the comparative example. Even if the concentration of the emulsifier was increased from 1 to 2%, based on the diesel fuel, phase separation was observed after 19 days (see Example 2).

Example 3: Use of the compounds according to the invention as corrosion-inhibiting additives

A 20 x 40 mm sheet of iron is blasted with 40 μm glass beads and then - based on ASTM D-665 - immersed in the emulsions prepared under Example 1 and stored at 40 ± 1 ° C for 24 hours. After 24 hours, the iron sheet is examined for rust formation. Here mean:

++ no rust formation; +0 slight rust;

-0 rust formation on more than 25% of the surface of the test sheet; Rust formation on more than 50% of the test sheet. As can be seen from the results in Table 2, only slight rust formation could be observed when using the compounds according to the invention as corrosion-inhibiting additives. In contrast, when using sorbitan monooleate (Comparative Examples 1 and 2), rust formation occurred on more than 25% of the surface of the test sheet.

Example 4: Use of the compounds according to the invention in fuels and their wear protection

The compounds B3, CI, Dl and D2 according to the invention were each individually dissolved in an unadditized diesel fuel (Miro, Karlsruhe). The concentration of additive in the diesel fuel was 75 ppm. The wear protection behavior was assessed using the HFRR test (High Frequency Roller Rig Test), which was carried out in accordance with ISO 12156-1. The length of the resulting grooves was measured and used as a measure of wear. The shorter the grooves, the better the wear protection of the additive added.

Table 3

For comparison, the scoring was observed when using unadditized diesel fuel and when using diesel fuel additized with C ₁₆ to C ₂₂ carboxylic acid mixture.

Claims

claims

1. Compound of the general formula I

0)

wherein R ¹ for an optionally substituted with -C ₁₂ alkyl substituted -Cs-alkylene or

C ₂ -C ₈ alkenylene, preferably an unsubstituted C -C ₄ alkylene,

R ² denotes a linear or branched C ₈ -C ₃₅₀ alkyl or C ₈ -C ₃₅₀ alkenyl, preferably a C ₂₂ -C ₃₅₀ polyisobutenyl,

R ³ and R ^{4 are} independently H, methyl or ethyl and together have no more than 2 C atoms,

R ⁵ and R ⁶ independently of one another are H, M ⁺ , SO ₃ H, SOsTVl ^{1 "} , PO ₃ H, PO ₃ T ^, and C (O) R ⁷ ,

where M ^{"1" stands} for NEW ⁺ , an alkali metal ion or 0.5 alkaline earth metal ions,

y and z are independently integers from 0 to 50, where R ⁵ = H if y = 0 and R ⁶ = H if z = 0.

2. Compound according to claim 1, characterized in that R ^{2 is} a polyisobutenyl with a number average molecular weight of 300 to 5000, preferably from 500 to 2300, particularly preferably from 500 to 1000.

3. A compound according to claim 1 or claim 2 with R ⁵ = R ⁶ = C (O) R ⁷ , characterized in that R of the general formula VI

(VI)

corresponds in which n is an integer from 1 to 4.

4. A process for the preparation of compounds (I) according to any one of claims 1 to 3

1 9 by reaction of dicarboxylic acids HO ₂ CR -CO ₂ H with amines R -NH ₂ and alkylene oxides of the general formula III in a suitable sequence,

R ³ "^^ R ⁴ (III)

and optionally by reacting the compound obtained in this way with SO ₃ , PO ₁₀ or with compounds R ⁷ C (O) OH

and then optionally with NH ₃ or (earth) alkali metal salts.

5. Compound of the general formula II

(II)

wherein R ^{1 is} an - optionally substituted with d-Cn-alkyl - -C ₈ alkylene or C ₂ - to C ₈ alkenylene, and

R ^{2 is} a linear or branched C ₈ -C ₃₅ o-alkyl or C ₈ -C ₃₅₀ alkenyl.

6. Compound of the general formula IV

(IV)

where R is a linear or branched C ₈ -C ₃ 5 ₀ -alkyl or C ₈ -C ₃ 5 ₀ -alkenyl,

R ³ and R ^{4 are} independently H, methyl or ethyl and together do not contain more than 2 carbon atoms, and

R ^{5 stands} for H, M ⁺ , SO ₃ H, SO ₃ Ts4 ⁺ , PO ₃ H, PO ₃ ^" M ⁺ , and C (O) R ⁷ ,

where M * is NH, an alkali metal ion or 0.5 alkaline earth metal ions, and

R ^{7 is} a linear C ₂ -C ₁₀ hydrocarbon radical substituted with at least one hydrophilic group.

, Compound of the general formula V

(V)

wherein R ¹ for an optionally substituted with Q-Cπ-alkyl CrCs alkylene or

C ₂ -C ₈ alkenylene,

R ² denotes a linear or branched C ₈ -C ₃₅₀ alkyl or C ₈ -C ₃₅ o-alkenyl,

R ⁵ and R ⁶ independently of one another represent H, M ⁺ , SO ₃ H, SOaTtf ^" , PO ₃ H, POsTV, and also C (O) R ⁷ ,

where M * is NH ₄ ⁺ , an alkali metal ion or 0.5 alkaline earth metal ions, and

8. Use of a compound according to any one of claims 1 to 3, preferably a compound in which R - R = H, as an emulsifier in the production of water-in-oil emulsions, the oil being a vegetable, animal or synthetic oil or Is fat.

9. Use of a compound according to one of claims 1 to 3, preferably a compound in which R ⁵ , R ⁶ ≠ H, as an emulsifier of a fuel in the production of water-in-fuel emulsions.

10. Water-in-fuel emulsion resulting from the use according to claim 9 and containing 60 to 95 wt .-% fuel, preferably diesel fuel, 3 to 35 wt .-% water and 0.2 to 10 wt .-%, preferably 0.5 to 5 wt .-%, a compound of the invention according to any one of claims 1 to 3, preferably a compound in which R ⁵ , R ⁶ ≠ H, as an emulsifier.

11. Emulsion according to claim 10, characterized in that, in addition to the compound according to the invention, one or more further emulsifiers, preferably sorbitan monooleate, C ₁₃ oxoalcohol ethoxylates or alkylphenol ethoxylates, are present.

12. A method for producing an emulsion according to claim 10 or 11, characterized in that the respective components are mixed together and emulsified in a manner known per se, preferably in a mixing nozzle.

13. Use of a compound according to any one of claims 1 to 3 as a surface-active substance, wear protection additive, lubricity-improving or corrosion-inhibiting additive in fuels, lubricants, fuel additive and lubricant additive concentrates or as a corrosion-inhibiting additive in aqueous liquids.

14. Fuel, lubricant, fuel additive concentrate, lubricant additive concentrate or aqueous liquid resulting from the use according to claim 13 and containing at least one compound according to one of claims 1 to 3.