DE10109845A1 - Emulsifiers, in particular based on polyisobutylene amines - Google Patents

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 R<1> represents a C1-C8-alkylene or a C2-C8-alkenylene optionally substituted with C1 -C12-alkyl; R<2> represents a linear or branched C8-C350-alkyl or a C8-C350-alkenyl; R<3> and R<4> independently represent H, methyl or ethyl and together do not have more than 2 C atoms; R<5> 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; R<7> 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 R<5> = H if y = 0 and R<6> = H if z = 0.

Description

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

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

For example, US-A 4,225,447 describes water-in-oil emulsions, which as Lubricants are used and a substituted with a polyisobutylenyl group Succinic anhydride, an (earth) alkali metal salt with a polyisobutylenyl group substituted succinic acid or one substituted with a polyisobutylenyl group Contain succinic acid amide as emulsifier.

From GB-A 2,157,744 drilling fluids are known which contain both an emulsifier, namely graft or block copolymers of polycarboxylic acids and polyethylene glycol, as also contain surfactants. Compounds are used as surfactants, which from a a polyisobutylenyl group substituted succinic anhydride and polyols, Polyamines, hydroxycarboxylic acids or amino alcohols are produced.  

EP-A 0 156 572 describes the use of anionic surfactants Substances based on succinic acid substituted with polyisobutylenyl groups derivatives for the preparation 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 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 ₄ 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, inter alia, the use of amides of the general formula R ¹ R ² NR ³ as emulsifiers in water-in-oil emulsions, where R ^{3 is} an acyl radical Mono- or polycarboxylic acid, and R ^{1 is derived,} inter alia, from a poly-1-butylene, -2-butylene or isobutylene or mixtures thereof, and R ^{2 can be} a polyalkylene-polyamine or a polyalkyleneimine radical.

Friction reducing additives for fuels and lubricants are as well 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 C ₁ to C ₆₀ alkyl, R ^{2 is} a C ₁ to C ₄ alkylene, a is an integer from 1 to 12 and R ^{3 is} C ₁ to C ₄ alkylene or substituted alkylene or cycloalkylene. Succinimides substituted with polyisobutylenyl 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 manufacture and / or product properties. at 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 be also in the production of emulsions result: often the emulsions have only one insufficient stability, so that phase separation occurs during storage. The The emulsifiers used must therefore be used in high concentrations, to allow the formation of a stable emulsion.

There is therefore a need for compounds that can be used as emulsifiers and do not have the disadvantages mentioned. Especially in the area of water Fuel emulsions are needed emulsifiers that are relatively stable emulsions generate and also a complete and largely residue-free Allow combustion of the fuel.

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

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

wherein R ¹ ₈ alkylene or C ₂ is optionally substituted with C ₁ -C ₁₂ -alkyl-substituted C ₁ -C - C-R ₈ 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 represent H, M ⁺ , SO ₃ H, SO ₃ ^- M ⁺ , OPO ₃ H, OPO ₃ ^- M ⁺ and C (O) R ⁷ ,
where M ^{+ is} NH ₄ ⁺ , an alkali metal ion or 0.5 alkaline earth metal ions,
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 compounds (I) according to the invention 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 vesicles can be produced under the action of ultrasound. The compounds of the invention are also applicable in a variety of ways, e.g. 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 methods are shown schematically in FIG. 1.

Fig. 1. A process for the preparation of compounds (I) with R ⁵ = R ⁶ = H.

Suitable reaction conditions for the amidation of the dicarboxylic acids HO ₂ CR ¹ -CO ₂ H with the amines R ² -NH 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 both in an organic solvent can also be implemented in substance. Suitable organic solvents are, for example, Solvesso® 150 from Shell and Isododecan.  

In a preferred embodiment of the process, the reaction is carried out under reduced pressure, for example at 5 to 50 mbar, and the resulting Water continuously distilled off during the reaction. A cleaning of the Bisamides (II) formed - before further implementation - are generally not necessary.

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 ⁵ = R ⁶ = 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, KtBuO, 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 phosphoric acid esters ((I) with R ⁵ = R ⁶ = OPO ₃ H) or with compounds HO ₂ CR ⁷ to esters ((I) with R ⁵ = R ⁶ = C (O) R ⁷ ) are implemented.

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 = SO ₃ ^- M ⁺ , or phosphates, can be obtained from the sulfuric acid esters or phosphoric acid esters, ( I) with R ⁵ = R ⁶ = OPO ₃ M ⁺ , where M ^{+ is} 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 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. Hydrophilic groups can also be introduced directly into the bisamides of the general formula V where R ⁵ = R ⁶ = H, as described in the previous section.

Dicarboxylic acids HO ₂ CR ¹ -CO ₂ H are used in which R ^{1 represents} a C ₁ -C ₈ alkylene or C ₂ -C ₈ alkenylene and is optionally substituted by C ₁ -C ₁₂ 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 ₁₂ -alkyl groups in any position. 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.

In general, amines R ² NH ₂ in which R ² is a linear or branched C _8-350 alkyl or C ₈ -C ₃₅₀ alkenyl C, for the preparation of compounds (I) in which R ⁵ = R ⁶ = H is suitable. "Alkenyl" also includes polyunsaturated hydrocarbon residues R ² .

Amines R ² -NH ₂ are preferably used, in which R ^{2 is} a C ₂₂ -C ₃₅₀ polyiso butylenyl.

Polyisobutylene amines R ² -NH ₂ with R ² = C ₂₂ -C ₃₅₀ polyisobutylenyl are from the ent speaking polyisobutylenes by standard methods, such as those described in DE-A 196 20 262, EP-A 0 244 616 and WO-A 97/03946 are described. The proportion of amino groups can be determined by titration with HCl 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 above Areas are preferably used that have a high vinylidene content have groups. In the context of the present invention, this means a  70 mol% of vinylidene groups, preferably a vinylidene group of 80 mol%, particularly preferably a proportion of vinylidene groups of ≧ 85 mol%.

Those polyisobutylenes which are number-average are particularly preferably used Molecular weight in the above ranges, a high content of Have vinylidene groups and a uniform polymer structure. examples for Polyisobutylenes with a uniform polymer structure are those polyisobutylenes at least 85% by weight, preferably at least 90% by weight, particularly preferred are made up of 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 von 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 _n of 2300.

Examples of commercially available polyisobutylene amines are those under Trade name Kerocom® PIBA compounds available from BASF AG.

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

For R ⁷ -CO ₂ H, compounds are used in which R ^{7 is} a linear C ₂ -C ₁₀ hydrocarbon radical substituted with at least one hydrophilic group. The term "C ₂ -C ₁₀ hydrocarbon radical" encompasses C ₂ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl and C ₇ -C ₁₀ alkylaryl. 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 = C ₁ -C ₆ alkyl, -CO ₂ H, -CO ₂ ^- _, OPO ₃ H, and OPO ₃ ^- . For R ⁷ -CO ₂ H compounds are preferably used, wherein R ⁷ 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.

In addition to L-amino acids, the corresponding D-amino acids or mixtures can also be used how the racemates of D and L amino acids are 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 Invention. There may be a purification of these compounds and theirs Intermediates necessary, for example when using these compounds as Emulsifiers for water-in-oil emulsions in the cosmetic or pharmaceutical sector.

The water-in-oil emulsions according to the invention generally contain 95 to 60 wt .-% oil, 3 to 35 wt .-% water and 0.2 to 10 wt .-% of an inventive Compound of general formula I.

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 is formed by a fuel, light or heavy heating oil. 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 C ₁ -C ₄ alcohols and / or monoethylene glycol, in particular monoethylene glycol. The amount of C ₁ -C ₄ alcohol and / or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water. The temperature range in which the emulsion is stable can be broadened, for example, by adding one or more C ₁ -C ₄ alcohols and / or monoethylene glycol.

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 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 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, as well as the block copolymers and ethylene copolymers such as ethylene oxide and ethylene oxide 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 grain is preferred for the water-in-fuel emulsions according to the invention combination of one or more of the above-mentioned further emulsifiers used with the emulsifiers according to the invention.  

If these further emulsifiers are used, this is done in amounts of 0.5 to 5 wt .-%, preferably 1 to 2.5 wt .-%, based on the total composition. The The amount of this further emulsifier is chosen so that the total amount of Emulsifier, ie emulsifier according to the invention plus further emulsifier, for the The amount of 0.2 to 10% by weight of the emulsifier according to the invention not given alone exceeds.

The selected one is used to prepare the water-in-oil emulsions according to the invention Emulsifier according to the invention with the oil, the water and the other, optional usable components mixed and emulsified in a conventional manner. For example, the emulsification in a rotor mixer, by mixing nozzle or by Ultrasound probe done. Particularly good results were achieved when one Mixing nozzle of the type used in the German application, File number: 198 56 604 of BASF AG from December 8, 1998. 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 also improve lubricity and corrosion effect on. 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 fluids used. This use is also the subject of present invention.

The compounds (I) according to the invention can be used as fuels and lubricants directly - together with other components. Alternatively, the Compounds (I) according to the invention first with other components to give fuel or Lubricant additive concentrates are mixed. This fuel according to the invention or lubricant additive concentrates can be undiluted or diluted with one or several solvents or carrier oils to the fuels or lubricants be added. The addition in dilute form is preferred.

The fuels, lubricants, fuel additive and lubricant additive concentrates, as well as aqueous liquids containing the compounds of the general invention  Contain formula I are also the subject of the present invention and are intended in following are explained in more detail.

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

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% by weight 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 of the invention 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.

Common components for fuels or fuel additive concentrates are for example additives with detergent action, as described in the German application BASF AG, file number 100 36 956.1, dated July 28, 2000 (page 14 ff.), In the German Registration of 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 are described. The additives mentioned there and other fuel additives described there with polar Groupings are also part of the present application and by Reference included.

In the fuels and fuel additive concentrates according to the invention can also Fuel additives, as described for example in the 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, 044 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 in one Amount of 0.01 to 3% by weight, based on the total weight of the concentrate, used.

Examples of further corrosion-inhibiting additives are those based on Film formation of ammonium salts of organic carboxylic acids or of heterocyclic aromatics for non-ferrous metal corrosion protection.

Examples of stabilizers are those based on amines such as p-phenylenediamine, Dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid.

Examples of organometallic compounds are ferrocene or methylcyclo pentadienylmangantricarbonyl.

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.

As a solvent for the fuel and lubricant according to the invention additive concentrates come like aliphatic and aromatic hydrocarbons Solvent naphtha, isododecane, mihagol, the fuels and lubricants themselves and carrier oils into consideration.

Carrier oils, also used to dilute the fuel and lubricant additive concentrates are used, for example mineral carrier oils (base oils), especially those in the viscosity class "Solvent Neutral (SN) 100 to 500", as well 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 ones 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. Also polyethylene oxides, polypropylene oxides, polybutene oxides and their Mixtures are suitable carrier oils. Other suitable carrier oils and carrier oil mixtures are described, for example, in the publications 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 according to the invention (I) optionally in combination with other customary corrosion inhibitors Additives, generally in a proportion of about 1 to 10 wt .-% - based on the Total quantity.

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 produced can be found in Table 1. As Polyisobutylenamine was used Kerocom® PIBA from BASF AG.

Synthesis of compounds A1, 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 A1 thus obtained was cooled and filled.

A4 was prepared analogously by reacting polyisobutylene amine (M _n = 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.

Synthesis of compound B1

282 g (approx. 130 mmol) of compound A1 and 3.95 g (35.2 mmol) of KtBuO were combined and at 100 ° C and 3 mbar volatile constituents on Rotary evaporator removed. The reaction mixture was in a 2 liter metal reactor submitted and then inerted three times with 5 bar nitrogen. The The reactor contents were heated to 120 ° C. and then 114 g within 60 min (2.59 mol) ethylene oxide metered in until a pressure of 5 bar was reached. It was until Stability of pressure stirred. After cooling and depressurizing the reactor Compound B1 obtained with a polyethylene glycol content of 5.2%.

Synthesis of compounds C1, 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 C1, 26 for C2 and 41 for C3. The products were neutralized discontinuously at 25 ° C. with 25% by weight aqueous NaOH solution.

Synthesis of D1

500 g of 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.

Synthesis of D2

Analogously to the synthesis of D1, the compound B1 was reacted with 45 g of L- Aspartic acid to 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 (C1, C2, C3, D1, D2, or D3) and 2 parts of a C ₁₃ oxo alcohol ethoxylate (Lutensol® TO 7 from BASF-AG) and composed of 2 parts from an alkylphenol ethoxylate (Emulan® OP 25). With an Ultra-Torrax® (Jahnke and Kunkel laboratory device T25) 500 g of this mixture were stirred with 100 ml water for 15 minutes at a speed of 24000 / min.

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

Table 2

The results in Table 2 show that the water-in-fuel Emulsions of the compounds according to the invention after 30 days of storage hardly Show signs of phase separation, while in the comparative example already was observed after 6 hours of phase separation. Even if the concentration of the Emulsifier from 1 to 2% - based on the diesel fuel - was increased after 19 days of phase separation observed (see Example 2).

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

A 20 × 40 mm iron sheet 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 area of the test sheet;
- Rust formation on more than 50% of the test sheet.

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

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

In an unadditized diesel fuel (Miro, Karlsruhe) the were individually Compounds B3, C1, D1 and D2 according to the invention dissolved. The concentration on Additive in diesel fuel was 75 ppm. Assessment of wear protection behaved by HFRR test (High Frequency Roller Rig Test), which according to ISO 12156-1 was carried out. The length of the resulting grooves was measured and as Measure of wear. The shorter the scoring, the better it was Wear protection of the added additive.

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 (14)

1. Compound of the general formula I
in which R ^{1 is} a C ₁ -C ₈ -alkylene or C ₂ -C ₈ -alkenylene which is optionally substituted by C ₁ -C ₁₂ -alkyl, preferably an unsubstituted C ₂ -C ₄ -alkylene,
R ^{2 is} a linear or branched C ₈ -C ₃₅₀ alkyl or C ₈ -C ₃₅₀ alkenyl, preferably a C ₂₂ -C ₃₅₀ polyisobutylenyl,
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 represent H, M ⁺ , SO ₃ H, SO ₃ ^- M ⁺ , OPO ₃ H, OPO ₃ ^- M ⁺ , and C (O) R ⁷ ,
where M ^{+ is} NH ₄ ⁺ , 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. 2. Compound according to claim 1, characterized in that R ^{2 is} a poly isobutylenyl 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 ^{7 of} the general formula VI
corresponds in which n is an integer from 1 to 4. 4. A process for the preparation of compounds (I) according to one of claims 1 to 3 by reacting dicarboxylic acids HO ₂ CR ¹ -CO ₂ H with amines R ² -NH ₂ and alkylene oxides of the general formula III in a suitable sequence,
and optionally by reacting the compound obtained in this way with SO ₃ , P ₄ O ₁₀ or with compounds R ⁷ C (O) OH and, if appropriate, subsequently with NH ₃ or (earth) alkali metal salts. 5. Compound of the general formula II
wherein R ^{1 is} a - optionally substituted with C ₁ -C ₁₂ alkyl - C ₁ -C ₈ alkylene or C ₂ - to C ₈ alkenylene, and
R ^{2 is} a linear or branched C ₈ -C ₃₅₀ alkyl or C ₈ -C ₃₅₀ alkenyl. 6. Compound of the general formula IV
where R ^{2 is} 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 together do not contain more than 2 carbon atoms, and
R ^{5 stands} for H, M ⁺ , SO ₃ H, SO ₃ ^- M ⁺ , OPO ₃ H, OPO ₃ ^- M ⁺ , and C (O) R ⁷ ,
where M ^{+ is} NH ₄ ⁺ , 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. 7. Compound of the general formula V
in which R ^{1 represents} a C ₁ -C ₈ alkylene or C ₂ -C ₈ alkenylene which is optionally substituted by C ₁ -C ₁₂ alkyl,
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 together do not contain more than 2 carbon atoms, and
R ⁵ and R ⁶ independently of one another represent H, M ⁺ , SO ₃ H, SO ₃ ^- M ⁺ , OPO ³ H, OPO ₃ ^- M ⁺ , and C (O) R ⁷ ,
where M ^{+ is} NH ₄ ⁺ , 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. 8. Use of a compound according to any one of claims 1 to 3, preferably a compound in which R ⁵ = R ⁶ = H, as an emulsifier in the production of water-in-oil emulsions, the oil being a vegetable, animal or synthetic table oil or 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 oxo alcohol ethoxylates or alkylphenol ethoxylates, are present. 12. A method for producing an emulsion according to claim 10 or 11, characterized characterized in that the respective components are mixed together and in at be emulsified in a known manner, preferably in a mixing nozzle. 13. Use of a compound according to any one of claims 1 to 3 as the upper 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 inhibitor Addition in aqueous liquids. 14. Fuel, lubricant, fuel additive concentrate, lubricant additive con 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.