DE10125158A1 - Low and high molecular weight emulsifiers, in particular on bases of polyisobutylene, and mixtures thereof - Google Patents

Abstract

The invention relates to low-molecular and high-molecular diblock emulsifiers, particularly based on polyisobutylene, of general formulas (Ia) and (Ib), and to mixtures thereof, whereby: L<a> represents a polyisobutylene group having a numerical average molecular weight Mn ranging from 300 to 1000; L<b> represents a polyisobutylene group having a numerical average molecular weight Mn ranging from 2000 to 20000; -A- represents -O-, -N(H)- or N(R<1>)-; M<+> represents H<+>, an alkali metal ion, 0.5 alkaline-earth metal ions or NH4<+>, whereby in NH4<+>, one or more H's can be substituted by alkyl radicals; R represents a linear or branched saturated hydrocarbon radical, which supports at least one substituent selected from the group consisting of OH, NH2 or NH3<+> and optionally supports one or more C(O)H groups while optionally containing one or more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH2 or NH3<+> groups, one or more H's can be substituted by alkyl radicals, and; R<1> represents a linear or branched saturated hydrocarbon radical, which optionally supports one or more substituents selected from the group consisting of OH, NH2, NH3<+> or C(O)H while optionally containing one or more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH2 or NH3<+> groups, one or more H's can be substituted by alkyl radicals, and the proportion of A-R on the compound of general formula (Ib) equals at least 20 wt. %.

Description

The present invention relates to low and high molecular weight compounds, in particular based on polyisobutylene, and mixtures thereof, which act as emulsions gates for water-in-oil emulsions are suitable, process for the preparation of such Compounds as well as the emulsions themselves.

The invention also relates to the use of such compounds as Additives for fuels and lubricants, as well as a corrosion inhibiting additive in water-containing liquids, as well as fuels, lubricants, fuel and lubricants Additive concentrates and water-containing liquids containing the Invention appropriate connections.

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 Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and a succinic anhydride substituted with an alkylenyl group (such as a polyisobutylenyl group), preferably with a number average molecular weight M _n of 300 to 3000 g / mol Contain (earth) alkali metal salt of a succinic acid substituted with an alkenyl group or a succinic acid amide substituted with an alkenyl group as an emulsifier, optionally in combination with the salt of a resin acid.

EP-A 0 156 572 describes the use of surface-active substances based on succinic acid derivatives substituted with polyisobutylenyl groups, preferably with a number average molecular weight M _n of 400 to 5000, with an anionic group for the preparation of water-in-oil or oil in-water emulsions. Suitable anionic groups are phosphate, phosphonate, sulfate, sulfonate and carboxymethyl groups.

The applicant's German application filed on January 25, 2000 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 applicant's German application filed 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 is a 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 polyalkylene imine radical.

WO 00/15740 discloses water-in-fuel emulsions which act as two emulsifiers succinic acid linked via a linker such as alkanolamine, polyamine or polyol contain derivatives with hydrocarbon radicals such as polyisobutylenyl groups are substituted, wherein in one embodiment a succinic acid derivative Polyisobutylenyl group with 8 to 25 carbon atoms and the other succinic acid derivative one Contains polyisobutylenyl group with 50 to 400 carbon atoms.

From GB-A 2,157,744 drilling fluids are known which contain both graft or block copolymers of polycarboxylic acids and polyethylene glycol, as well as compounds which consist of a succinic anhydride substituted with a polyisobutylenyl group, preferably with a number average molecular weight M _n of 400 to 5000, and polyols , Polyamines, hydroxycarboxylic acids or amino alcohols.

No. 4,708,753 discloses water-in-fuel emulsions which contain, inter alia, mono- or disalts of succinic acid with amines or amine salts of succinic acid monoesters as emulsifiers. These salts are formed by reacting alkanolamines, polyamines, oligoalcohols or polyols with succinic anhydrides which are substituted with C ₂₀ -C ₅₀₀ hydrocarbon radicals such as polyisobutylenyl groups. In the examples only the salts of succinic acids or their monoesters are described which carry a polyisobutylenyl group with a number average molecular weight of 950 or 1700.

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 (-OR ² -) _a NH (CO) -R ³ -OH being used in particular as friction-reducing additives, wherein R ¹ 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 that, if not removed, set the same as one difficult to maintain the viscosity of the emulsifier. Disadvantages can also arise 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 To provide which are used as emulsifiers in water-in-oil emulsions can.

The above object is achieved by compounds of the general formulas (Ia) and (Ib)

where L ^{a stands} for a polyisobutylenyl group with a number average molecular weight M _n of 300 to 1000,
L ^{b represents} a polyisobutylenyl group with a number average molecular weight M _n of 2,000 to 20,000,
-A- stands for -O-, -N (H) - or -N (R ¹ ) -,
M ^{+ represents} H ⁺ , an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ⁺ , where one or more H in NH ₄ ⁺ can be replaced by alkyl radicals,
R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (H) O groups and optionally non-adjacent -O- and / or -N (H) - and / or tertiary

contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
R ^{1 represents} a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (H) O and optionally non-adjacent -O- and / or -N ( H) - and / or tertiary

contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
the proportion of AR in the compound of the general formula (Ia) or (Ib) is at least 20% by weight.

Compounds of the general formula (Ia) in which the proportion of the hydrophilic radical A- R at lower values such as 5.2 to 15.2% by weight are known per se and will be in GB-A 2,157,744 and US 4,708,753. However, it does not include the advantageous properties recognized as an emulsifier in the inventive Connections with an A-R content of ≧ 20% by weight occur.

The compounds of the invention can be used either individually or in a mixture Emulsifiers can be used in water-in-oil emulsions. It can be more stable Generate emulsions than when using conventional emulsifiers.

In particular, the compounds of the general formula (Ib) can be regarded as diblock emulsifiers linked via a linker, the lipophilic block L ^a or L ^b via a covalent CC bond and the hydrophilic block R or R ¹ via an ester or amide bond is linked to the left succinic acid.

Preferred compounds of the general formula (Ia) are those in which

• - L ^{a stands} for a polyisobutylenyl group with a number average molecular weight M _n from 350 to 950, in particular from 350 to 650, and / or
• L ^{a stands} for a polyisobutylenyl group which has a polydispersity ≦ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
• The proportion of A-R in the compound of the general formula (Ia) is at least 25% by weight, is in particular 35 to 60% by weight, and / or
• R is composed of [-CH ₂ -CH ₂ -X] -, [-CH (CH ₃ ) -CH ₂ -X] - and / or [-CH ₂ -CH (CH ₃ ) -X] units, with X = O or NH.

Preferred compounds of the general formula (Ib) are those in which

• L ^{b stands} for a polyisobutylenyl group with a number average molecular weight from 2000 to 12000, in particular from 2300 to 5000, and / or
• L ^{b stands} for a polyisobutylenyl group which has a polydispersity ≦ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
• The proportion of A-R in the compound of the general formula (Ib) is at least 25% by weight, is in particular 35 to 60% by weight, and / or
• R is composed of [-CH ₂ -CH ₂ -X] -, [-CH (CH ₃ ) -CH ₂ -X] - and / or [-CH ₂ -CH (CH ₃ ) -X] units, with X = O or NH.

Compounds of the general formula (Ia) or (Ib) in which A = -O- and R is a monovalent radical of an oligomer or polymer of ethylene and / or propylene oxide or a monovalent residue of a block copolymer of ethylene and is propylene oxide.

Particularly effective emulsifiers are compounds of the general formula (Ia) in which L ^{a stands} for a polyisobutylenyl group with a number-average molecular weight M _n of 350 to 950, in particular 350 to 650, this polyisobutylenyl group optionally having a polydispersity, 3.0 from 1.1 to 2.5, particularly preferably from 1.1 to 2.0.

It has been shown that the total amount of emulsifier for the preparation of stable emulsions can be reduced if
a mixture containing as emulsifier is used

• a) at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of the general formula (Ia),
  
• b) at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general formula (Ib),
  where L ^{a is} a polyisobutylenyl group with a number average molecular weight M _n of 300 to 1000 and L ^{b is} a polyisobutylenyl group with a number average molecular weight M _n of 2000 to 20,000,
  -A- stands for -O-, -N (H) - or -N (R ¹ ) -,
  M ^{+ represents} H ⁺ , an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ⁺ , where one or more H in NH ₄ ⁺ can be replaced by alkyl radicals,
  R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (H) O groups and optionally non-adjacent -O- and / or -N (H) - and / or tertiary
  contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
  R ^{1 stands} for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (H) O and optionally non-adjacent -O- and / or - N ( H) - and / or tertiary
  contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
  the proportion of AR in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) is at least 20% by weight.

Effective emulsifier mixtures are not only used when using the general formula (Ia) with hydrophilic proportions of at least 20 wt .-%, but even when using compounds of general formula (Ia) with hydrophilic components of at least 10% by weight.

Mixtures according to the invention are preferred which, in addition to at least one compound of the general formula (Ib), contain at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of contain general formula (Ia) in which L ^{a is} a polyisobutylenyl group with a number average molecular weight M _n of 350 to 950, in particular 350 to 650, and / or the proportion of AR in the compound of general formula (Ia) is at least 15% by weight %, preferably at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably 35 to 60% by weight.

Preference is also given to mixtures according to the invention which, in addition to at least one compound of the general formula (Ia), at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general Contain formula (Ib) in which L ^{b is} a polyisobutylenyl group with a number average molecular weight M _n from 2000 to 12000, in particular from 2300 to 5000, and / or the proportion of AR in the compound of the general formula (Ib) is at least 25% by weight. -%, in particular 35 to 60 wt .-%, is.

The present invention also relates to processes for the preparation of the compounds of the general formula (Ia) or (Ib). Here, polyisobutylene with fumaryl, fumaric acid, maleic acid, maleic anhydride or maleic acid, preferably with maleic anhydride or maleic, more preferably with maleic anhydride, to give succinic acid derivatives of the general formula (IIa), (IIb) or (IIc), wherein L ^a is a polyisobutylenyl with a numbers average molecular weight M _n of 300 to 1000 and L ^{b is} a polyisobutylenyl group with a number average molecular weight M _n of 2000 to 20,000.

The reaction takes place according to the methods known to the person skilled in the art and, for example analogous to that in the German laid-open documents DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672 processes for the reaction of polyisobutylenes with Maleic anhydride.

The number average molecular weight M _{n of} the resulting succinic anhydride derivative, which is substituted by a polyisobutylenyl group, can be characterized by the saponification number [mg KOH / g substance].

The substituted succinic acid derivatives of the general formulas (IIa) and (IIb) are then reacted with polar reaction partners ROH or RR ¹ NH by processes known to the person skilled in the art,
where R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (H) O groups and optionally non-adjacent -O- and / or -N (H) - and / or tertiary

contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
R ^{1 represents} a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (H) O and optionally non-adjacent -O- and / or -N ( H) - and / or tertiary

contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals.

The alkyl radicals which can replace the H atoms are C ₁ -C ₄ alkyl radicals.

Examples of suitable polar reactants ROH and RR ¹ NH are alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols as well as carbohydrates and sugar. Polar reactants can also be ethylene oxide and / or propylene oxide. The reaction with polyethylene glycol, polypropylene glycol, their (block) copolymers, ethylene oxide or propylene oxide is preferred. For the preparation of low molecular weight compounds of the general formula (Ia), reaction with alkanolamines such as di- / triethanolamine, tris (hydroxymethyl) amino methane and their salts, oligoalcohols such as sorbitol and pentaerythritol or carbohydrates and sugars is also preferred. The reaction with tris (hydroxymethyl) aminomethane, choline, sugars and polyethylene glycol is particularly preferred for the preparation of compounds of the general formula (Ia).

The amount of the polar reactant is chosen so that the proportion of the hydrophilic Radical A-R on the compound of general formula (Ia) or (Ib) at least 20% by weight, is preferably 25% by weight, particularly preferably 35 to 60% by weight. Also Compounds of the general formula (Ia) in which the hydrophilic content is 10 to 20% by weight lies, can be produced according to the described processes. The Conversion ratio of the substituted succinic acid derivatives (IIa), (IIb) or (IIc) the alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols or Polyalkylene glycols is generally 1: (0.75 to 2), preferably 1: (0.8 to 1.2), particularly preferably 1: 1. In the reaction with ethylene oxide and / or propylene oxide the amount of ethylene and / or propylene oxide according to the desired chain length of the hydrophilic radical A-R selected.

Compounds of the general formula (Ia) or (Ib) in which A = -O- and R. monovalent residue of an oligomer or polymer of ethylene and / or propylene oxide or is a monovalent residue of a block copolymer of ethylene and propylene oxide, can be implemented both by reacting polyethylene glycol, polypropylene glycol or their (block) copolymers with the substituted succinic acid derivatives (IIa), (IIb) or (IIc) obtained, as well as by reacting ethylene oxide and / or propylene oxide with the substituted succinic acid derivatives (IIa), (IIb) or (IIc).

By reacting the substituted succinic acid derivatives (IIa), (IIb) or (IIc) with the polar reactants mentioned, succinic acid semiesters or half amides are obtained. When alkanolamines are used, the hydroxyl and / or amino groups react, so that mixtures of succinic acid half-esters and succinic acid halamides are generally obtained. If maleic or fumaric acid dichloride is used as the starting material, the C (O) Cl group still present after the reaction steps mentioned is hydrolyzed to the CO ₂ H group. The free CO ₂ H group present in the succinic acid half-esters and half-amides can then be reacted with NH ₃ , amines, alkali metal or alkaline earth metal salts to give the corresponding amine, alkali metal or alkaline earth metal salts. These salts are compounds of the general formula (Ia) or (Ib), in which M ^{+ represents} an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ⁺ , one or more H in NH ₄ ^{+ being} replaced by alkyl radicals could be. Suitable amines for salt formation are primary, secondary and tertiary amines which carry linear C ₁ -C ₄ or branched C ₃ -C ₆ alkyl groups. These alkyl groups can also be substituted with one or more hydroxyl groups. Examples of suitable alkylamines are diethylamine, diisopropylamine, trimethylamine, mono-, di- and triethanolamine and tris (hydroxymethyl) aminomethane.

In general, polyisobutylenes with a number average molecular weight M _n of 300 to 1000, preferably from 350 to 950, particularly preferably from 350 to 650, are used to prepare the compounds of the general formula (Ia).

For the preparation of the compounds of the general formula (Ib), polyisobutylenes with a number average molecular weight M _n of 2,000 to 20,000, preferably from 2,000 to 12,000, particularly preferably from 2,300 to 5,000, are generally used.

Of the polyisobutylenes with a number-average molecular weight M _n 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 of ≧ 80 mol%, particularly preferably of ≧ 85 mol%.

Those polyisobutylenes which have a number-average molecular weight M _n in the abovementioned ranges, a high content of vinylidene groups and a uniform polymer skeleton structure are particularly preferably used. In the context of the present invention, this means polyisobutylenes which are composed of at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of isobutylene units.

Very particularly preferred are polyisobutylenes with a number-average molecular weight M _n in the ranges mentioned, a high content of vinylidene groups and a uniform structure, which have a polydispersity ≦ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 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 .

Polyisobutylenes with a number-average molecular weight M _n 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 suitable alkanolamines, polyamines, oligo alcohols, polyols and Polyalkylene glycols used to prepare the compounds of the invention can be described in WO 00/15740.

Examples of alkanolamines are monoethanolamine, diethanolamine, 2-amino-1-butanol, 2- Amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3- propanediol, N- (2-hydroxypropyl) -N '- (2-aminoethyl) piperazine, tris (hydroxymethyl) amino methane, 2-amino-1-butanol, β- (2-hydroxyethoxy) ethylamine, glucamine, glucosamine, 4- Amino-3-hydroxy-3-methyl-1-butene, N- (3-aminopropyl) -4- (2-hydroxyethyl) piperidine, 2- Amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N- (2-hydroxyethyl) -1,3- diaminopropane, 1,3-diamino-2-hydroxypropane, N- (2-hydroxyethyl) ethylenediamine, N, N- Bis (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethoxyethyl) ethylenediamine, 1- (2- Hydroxyethyl) piperazine, monohydroxypropyl substituted diethylene triamine, dihydroxy propyl substituted tetraethylene pentamine and N- (3-hydroxybutyl) tetramethylene diamine.

The salts of the alkanolamines mentioned can also be used. In these salts, one or more of the H atoms bound to N atoms can optionally be replaced by linear C ₁ -C ₆ alkyl or branched C ₃ -C ₆ alkyl groups. Choline may be mentioned as an example.

Examples of suitable polyamines are polyalkylene polyamines such as polymethylene polyamines, polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and Polypentylenpolyamine; see also "Ethylene Amines" in Kirk Othmer's "Encyclopedia of Chemical Technology ", 2nd edition, volume 7, pp. 22-37, Interscience Publishers, New York 1965th

Examples of suitable oligoalcohols and polyols are 1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol, 1,2-cyclohexanediol, (mono-, di-) - pentaerythritol, 1.7 - and 2,4- heptanediol, 1,2,3-, 1,2,4-, 1,2,5- and 2,3,4-hexanetriol, 1,2,3- and 1,2,4- Butanetriol, 2,2,6,6-tetrakis (hydroxymethyl) cyclohexanol, 1,10-decanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-hydroxymethyl-2-ethyl-1,3-propanediol, Sorbitol, mannitol and inositol. C ₅ and C ₆ sugars such as glucose and fructose are also suitable.

Examples of (oligo) alkylene glycols are (tri-, tetra-, penta, hexa-) ethylene glycol, (tri-, Tetra-, penta, hexa-) propylene glycol and (tri-, tetra-, penta, hexa-) butylene glycol.

Examples of polyalkylene glycols are polytetrahydrofuran, polyethylene glycol and polypropylene glycol. Preferred polyalkylene glycols are polyethylene glycol and polypropylene glycol. Polyethylene glycol and polypropylene glycol and their block copolymers are particularly preferably used, which have a number average molecular weight M _n of 300 to 5000, preferably 300 to 2000, particularly preferably 500 to 1500.

Such polyethylene glycols are available, for example, under the trade name Pluriol® E from BASF AG, such as Pluriol® E 300 with an M _n of 300, Pluriol® E 600 with an M _n of 600, Pluriol® E 4000 with an M _n of 4000 and Pluriol®® E 5000 with an M _n of 5000. Polyethylene-polypropylene glycol block copolymers are available, for example, under the trade name Pluronic® PE from BASF AG, such as Pluronic® PE 3500 with an M _n of 1900 and an ethylene oxide content of 50%. -%.

Are the compounds of the invention and / or the inventive Mixtures used in oil-in-water emulsions, so stable vesicles produce. This can be done, for example, by the action of ultrasound. The compounds of the invention and / or the mixtures of the invention also applicable in a variety of ways, e.g. B. as additives in fuels and Lubricants, as a corrosion-inhibiting additive in water-containing liquids as well as dispersants for inorganic and organic solid dispersions. The compounds according to the invention and / or the mixtures according to the invention are also used as surfactants for washing and cleaning formulations. to Stabilization of inorganic and organic solid dispersions are particularly important high molecular weight compounds of the general formula (Tb) suitable, the contain monovalent residue of a polyethylene glycol as a hydrophilic block.

The compounds according to the invention and / or mixtures according to the invention are suitable also as emulsifiers for water-in-oil emulsions, in which the oil phase of a vegetable, animal or synthetic oil or fat is formed. such Emulsions are used in the cosmetic or pharmaceutical field. Examples  for such oils or fats are triglycerides and glycol esters of lauric acid, myristic acid, Stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.

The compounds according to the invention and / or are particularly advantageous mixtures according to the invention are used as emulsifiers for water-in-oil emulsions, where the oil phase is formed by a fuel, light or heavy fuel oil becomes. All common types of fuel can be used, for example Diesel fuel, petrol and kerosene. Diesel fuel is preferably used.

In general, the compounds according to the invention and theirs are purified Intermediate products not necessary; only for certain applications, for example when using these compounds as emulsifiers for water-in-oil Emulsions in the cosmetics or pharmaceutical field can, if appropriate Purification may be necessary.

The use of compounds according to the invention and / or according to the invention Mixtures as emulsifiers in the manufacture of water-in-oil emulsions is also Subject of the invention as the water-in-oil emulsions themselves Water-in-oil emulsions generally contain 95 to 60% by weight oil, 3 to 35% by weight % Water and 0.2 to 10% by weight of at least one compound according to the invention and / or a mixture according to the invention.

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 block copolymers such as ethylene oxide and copolymers of ethylene oxide and propylene copolymers 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 compounds according to the invention and / or mixtures thereof.

If these further emulsifiers are used, this takes place in amounts of 0.5 to 5% by weight, preferably 1 to 2.5% by weight, based on the total composition. The The amount of this further emulsifier is chosen so that the total amount of Emulsifier for the compounds according to the invention and / or their mixtures the amount specified alone does not exceed 0.2 to 10% by weight.

To prepare the water-in-oil emulsions according to the invention, the compounds according to the invention and / or mixtures according to the invention with the oil, mixed with the water and other optional components and in emulsified in a known manner. For example, the emulsification in one Rotor mixers, using a mixing nozzle or an ultrasonic probe. Particularly good ones Results have been obtained when using a mixing nozzle of the type shown in the German registration, file number: 198 56 604 of the applicant dated December 8, 1998 is disclosed. Water-in-oil emulsions for the cosmetics sector can also be used produce like water-in-fuel emulsions.

The compounds according to the invention and / or mixtures according to the invention have in addition to their surface-active, surface-active and emulsifying properties also has a lubricity-improving and corrosion-inhibiting effect. moreover improve the wear protection behavior of liquids. Therefore, the Compounds according to the invention and / or mixtures according to the invention as additives  for lubricants, fuels and water-containing liquids such as coolant liquids or drilling and cutting fluids are used. This use is also Subject of the present invention.

The compounds according to the invention can be used for fuels and lubricants and / or mixtures according to the invention directly - together with other components - be added. Alternatively, the compounds according to the invention and / or mixtures 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 water-containing liquids containing the compounds according to the invention and / or Contain mixtures according to the invention are also the subject of the present Invention and are to 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 and / or one according to the invention Mixture 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% by weight at least one compound according to the invention and / or one according to the invention Mix, 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 and / or a mixture according to the invention in proportions of 0.1 to 80 wt .-%, in particular of 0.5 to 60 wt .-%, 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  Applicant, file number 100 36 956.1, dated July 28, 2000 (page 14 ff.), In German Registration of the applicant, file number 100 03 105.6, dated January 25, 2000 and in the PCT- Application of the applicant with the file number PCT / EP / 01/00496 are described. The additives mentioned there and other fuel additives described there with polar Groupings are part of the present application and by reference locked in.

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, 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 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.

Suitable solvents for the fuel and lubricant additive concentrates according to the invention are aliphatic and aromatic hydrocarbons such as solvent naphtha, isododecane, mihagol (a technical mixture of C ₁₀ -C ₁₂ paraffins), 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 M _n of 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.

Water-containing liquids according to the invention contain the liquids according to the invention Compounds and / or mixtures according to the invention, if appropriate in combination with other conventional corrosion-inhibiting additives, generally in one proportion from about 1 to 10 wt .-% - 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 the general formula (Ia) and (Ib)

The composition of the compounds produced can be found in Table 1.  

As polyisobutylene, Glissopal® from BASF AG with a number average molecular weight M _n of 380 to 8400, a proportion of vinylidene end groups of <70 mol%, a polydispersity M _w / M _n in the range from 1.15 to 1.8 and one Polymer scaffold structure with more than 85% isobutylene units used. This polyisobutylene served as the starting material for the synthesis of succinic anhydride (PIBSA; = polyiso butylene succinic anhydride) substituted with a polyisobutylenyl group.

Pluriol® E from BASF AG with a number average molecular weight M _n of 300 to 5000 was used as the polyethylene glycol. Pluronic® PE 3500 from BASF AG with a number-average molecular weight M _n of 1900 and an ethylene oxide content of 50% by weight was used as the polyethylene / polypropylene glycol block copolymer.

Heptane, Mihagol, a mixture of C ₁₀ -C ₁₂ paraffins from Wintershall, and Solvesso® 150, a mixture of aromatic hydrocarbons from ExxonMobil Chemical, were used as solvents.

The ion exchanger was the one commercially available under the name Ambossol® from Clariant.

Maleination of the polyisobutylenes to the corresponding succinic anhydrides was carried out according to methods known per se and is described, for example, in DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672 are described.

The compounds obtained were determined via the acid number, the OH number and the viscosity and / or characterized the IR spectra. The OH number was in use high-boiling solvent determined solvent-adjusted, d. H. that the OH number of the Compounds measured in the respective solvent and then on the pure substance was extrapolated. With low-boiling solvents such as heptane, the solution removed by distillation, and the OH number determined from the pure substance.

The viscosities were always determined in accordance with DIN 51562.  

Table 1

Composition of the compounds of the general formula (Ia) or (Ib)

Preparation of compound A

A 1 l four-necked flask with stirrer, dropping funnel and thermocouple is made with 250 g PIBSA 550 filled and heated to 90 ° C. 67 g of diethanolamine are added via a dropping funnel dosed within 5 minutes. The mixture is gradually heated to 130 ° C or 170 ° C. After 2 hours at 170 ° C, the brown reaction product is filtered at 100 ° C.

Preparation of compound B

A 2 l four-necked flask with stirrer, distillation bridge and thermocouple is made with 525 g PIBSA 550, 650 g Solvesso® 150 and 175 g trihydroxymethylaminomethane (TRIS) filled. The mixture is gradually heated to 130 ° C or 170 ° C. liberated  Water is removed using a stream of nitrogen; the reaction time is 3 hours. The OH The number was determined to be 250 when adjusted for solvents.

Preparation of compound C

A 1 l four-necked flask with stirrer, distillation bridge and thermocouple is at 310 g PIBSA 750 and 60 g D-sorbitol filled. The mixture is gradually increased to 160 ° C or Heated to 220 ° C. Released water is removed using a stream of nitrogen; after 3 hours at 220 ° C is diluted with 200 g of Mihagol and filtered hot. You get a yellow, viscous product solution (65%).

Preparation of compound D

A 2 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 350 g Pluriol® E 300 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 650 g of PIBSA 380 in 350 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., a yellow product with a viscosity of 105 mm ² / s (100 ° C.) is obtained; OH number: 70, acid number: 73; IR: intense band at 1735 cm ^-1 (ester).

Establishing connection E

A 2 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g Pluriol® E 300 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 750 g of PIBSA 550 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C, 105 g of diethanolamine are added in portions at 95 ° C. After a further 20 minutes at 95 ° C, the orange-brown product is filtered hot. OH number: 55; IR: intense band at 1736 cm ^-1 (ester).

Establishing connection F

A 2 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 400 g Pluriol® E 600 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 790 g of PIBSA 1000 in 450 g of heptane is metered in via a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., a yellow product with a viscosity of 1650 mm ² / s (100 ° C.) is obtained. OH number: 43; SZ: 40; IR: intense band at 1734 cm ^-1 (ester).

Establishing compound G

A 1 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 150 g Pluriol® E 1500 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 280 g PIBSA 2300 in 300 g Mihagol is dosed within 5 minutes at 80 ° C using a dropping funnel. The mixture is gradually heated to 110 ° C or 140 ° C. After 3 hours at 140 ° C, a yellow, highly viscous product solution is obtained. Viscosity 1750 mm ² / s, 100 ° C; OH number: 9; SZ: 8.1; IR: band at 1736 cm ^-1 .

Preparation of compound H

A 1 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 150 g Pluriol® E 4000 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 250 g PIBSA 5200 in 300 g Mihagol is dosed within 5 minutes at 80 ° C using a dropping funnel. The mixture is gradually heated to 110 ° C or 140 ° C. After 3 hours at 140 ° C, a beige wax is obtained. OH number: 4.3; SZ: 3.5; IR: band at 1736 cm ^-1 (ester).

Preparation of compound I

The synthesis is carried out analogously to the synthesis of the compound H from PIBSA (basis: reactive PIB 8400; M _w / M _n = 1.45) and Pluriol® E 5000. The product is isolated as a cream-colored wax (60% in Mihagol); IR: 1737 cm ^-1 .

Preparation of Compound J for Comparative Example 1

The synthesis is carried out analogously to the synthesis of compound A from PIBSA 1000 (basis: reactive PIB 1000; M _w / M _n = 1.31) and diethanolamine (see also US Pat. No. 4,708,753). The product is isolated as a brown, highly viscous liquid and has a lower hydrophilic content of AR than compound A.

Establishing the connection K

The synthesis is carried out analogously to the synthesis of compound F from PIBSA 1000 (basis: reactive PIB 1000; M _w / M _n = 1.31) and Pluronic® PE 3500. The product is isolated as an orange-yellow, highly viscous liquid. Viscosity: 2100 mm ² / s; 100 ° C.

Production of the connection L

A 1 l four-necked flask with stirrer, dropping funnel and thermocouple becomes one with 75 g 45% methanol solution of choline from Fluka and 150 g of Mihagol filled. Methanol is then removed at 50 ° C and reduced pressure (50 mbar) (45 Minutes). 200 g of PIBSA 550 are metered into this suspension and heated within 15 minutes at 90 ° C. After 60 minutes, the temperature is raised to 170 ° C. and for a further two hours touched. The brown reaction product is filtered at 100 ° C.

Preparation of compound M for comparative example 2

A 1 l four-necked flask with stirrer, dropping funnel and thermocouple is at 300 g PIBSA 2300, 200 g PIBSA 1000 and 200 g Mihagol filled and heated to 95 ° C. at At 95 ° C, 17.2 g of ethylene glycol are metered in. The mixture is heated to 130 ° C and at this temperature stirred for three hours. The brown reaction product is at 100 ° C filtered.  

The emulsifier of Comparative Example 2 was based on the principle of WO 00/15740 Example C-1, p. 34.

Preparation of compound N for comparative example 3

(The preparation is carried out analogously to compound F. However, compound F contains one Share A-R of 35.3%, while in compound N the hydrophilic share A-R 15.4% is.)

A 2 l four-necked flask with stirrer, dropping funnel and thermocouple is filled with 100 g Pluriol® E 200 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 590 g of PIBSA 1000 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., an amber-colored product with a viscosity of 1450 mm ² / s (100 ° C.) is obtained.

Example 2 Production of water-in-fuel emulsions

The production or the composition of the fuel mixtures is shown in Table 2 compiled.

The hydrophilic or water-soluble components were previously in the aqueous phase dissolved, lipophilic components in diesel oil. With an Ultra-Turrax® (Jahnke and Kunkel Laboratory device T25) was 500 g of this mixture with 100 ml of water for 15 minutes with a Homogenised speed of 24000 / min. The preparation of the emulsion in The technical scale and the motor tests were carried out analogously to DE-A 198 56 604 Applicant (registered on December 8, 1998) with a mixing nozzle described there. The Pressure in the mixing apparatus with a conversion of (total) 12 kg / h was 50 to 200 bar (before the aperture), preferably 120 bar.  

In Examples 1, 2, 6 and 7, low molecular weight compounds according to the invention, In Examples 3, 4 and 5, mixtures of low and high molecular compounds used.

Table 2

Composition of the emulsions

Example 3 Studies on the stability of water-in-fuel emulsions

The size of the water drops was physically determined by laser diffraction (X3.2 values) using a Malvern Mastersizer 2000 from Malvern Instruments GmbH. The measurement method is described for example in Terence Allen, Particle Size Measurement, Volume 1, ^5th Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999. Depending on the actually existing size distribution in addition to the laser light scattering methods or other such arrive. B. the dynamic light scattering, single particle counter and ultrasonic extinction in question.

The size of the water drops is a measure of the quality of the emulsion. The smaller the Drop size, the better or more stable the emulsion. The corresponding values for the drop size (the X3.2 values) are summarized in Table 3. As in Table 3 can be seen, the emulsions using the inventive Compounds and the mixtures according to the invention, in some cases significantly smaller Drop sizes on than the comparative emulsions. That the drop size is really a measure for the stability of the emulsion at room temperature is shown by the Storage tests determined values for stability. The emulsions with larger ones Drop sizes also have poorer storage stability.

Table 3

Drop size and stability of the water-in-fuel emulsions

The stability of the emulsions was tested in a static storage test at 20 ° C (12 weeks long) and additionally under changing temperatures (-20 ° C and 70 ° C, 1 week each long) checked. For this, the emulsion was placed in a scaled 100 ml standing cylinder filled and visually inspected for their quality according to the specified conditions.

Compared to the use of emulsifiers from the prior art (comparative examples) is using the emulsifiers according to the invention and their mixtures to observe a sometimes significant improvement in storage stability. The The storage tests at -20 ° C were then assessed at room temperature. The After thawing, the emulsion according to Example 2 is also without an anti-freeze additive (e.g. Monoethylene glycol) comparatively homogeneous. Otherwise, has already been done when heated, a phase separation, a so-called "breaking" of the emulsion.

A comparison of the quality of the emulsions according to the invention with an emulsion after WO 00/15740 (Example C-1, p. 34, Comparative Example 2) proves that a Kombina tion of a low molecular weight component and a higher molecular weight component a correspondingly bridged connection to a significantly worse emulsifier performs as a mixture of the isolated compounds according to the invention.

Example 4 Use of the compounds of the general Formula (I) as rust and wear protection 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 in Example 2 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 formation;
-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 4, when using the compounds according to the invention as corrosion-inhibiting additives, in some cases only slight rust formation was observed. In contrast, rust formation occurred on more than 50% of the surface of the test panel when using C ₁₃ oxo alcohol ethoxylate.

Example 5 Use of the compounds of the general Formula (I) in fuels and their wear protection behavior

In an unadditized diesel fuel (Miro, Karlsruhe) were the Solved compounds listed in the table. The concentration of additive in the Diesel fuel was 75 ppm. The wear protection behavior was assessed via HFRR test (High Frequency Roller Rig Test), which is carried out in accordance with ISO 12156-1 has been. The length of the resulting grooves was measured and used as a measure for the Wear used. The shorter the scoring, the better it was Wear protection of the added additive. For comparison, non-additive diesel Fuel used. As can be seen in Table 4, the inventive protect Connections before wear.

Table 4

Claims (16)

1. Compound of the general formula (Ia) and (Ib)
where L ^{a represents} a polyisobutylenyl group with a number average molecular weight M _n of 300 to 1000,
L ^{b stands} for a polyisobutylenyl group with a number average molecular weight M _n of 2,000 to 20,000,
-A- stands for -O-, -N (H) - or -N (R ¹ ) -,
M ^{+ stands} for H ⁺ , an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ⁺ , it being possible for one or more H in NH ₄ ^{+ to be} replaced by alkyl radicals, and
R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (H) O groups and optionally non-adjacent -O- and / or -N (H) - and / or tertiary
contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
R ^{1 stands} for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (H) O and optionally non-adjacent -O- and / or - N ( H) - and / or tertiary
contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
the proportion of AR in the compound of the general formula (Ia) or (Ib) is at least 20% by weight. 2. Compound according to claim 1, characterized in that L ^a for a polyisobutylenyl group with a number average molecular weight M _n from 350 to 950, in particular from 350 to 650, and L ^b for a polyisobutylenyl group with a number average molecular weight from 2000 to 12000, in particular from 2300 to 5000. 3. Compound according to claim 1 or 2, characterized in that L ^a and L ^{b represent} a polyisobutylenyl group which has a polydispersity ≦ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2, 0. 4. A compound according to any one of claims 1 to 3, characterized in that L ^a and L ^{b represent} a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units. 5. Connection according to one of claims 1 to 4, characterized in that the Proportion of A-R in the compound of the general formula (Ia) and (Ib) is at least 25% by weight, in particular 35 to 60% by weight. 6. Connection according to one of claims 1 to 5, characterized in that A = - O and R is a monovalent residue of an oligomer or polymer of Ethylene oxide and / or propylene oxide or a monovalent residue of a block copoly mer of ethylene and propylene oxide. 7. Containing mixture

• a) at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of the general formula (Ia),
  
• b) at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general formula (Ib),
  where L ^{a is} a polyisobutylenyl group with a number average molecular weight M _n of 300 to 1000 and L ^{b is} a polyisobutylenyl group with a number average molecular weight M _n of 2000 to 20,000,
  -A- stands for -O-, -N (H) - or -N (R ¹ ) -,
  M ^{+ represents} H ⁺ , an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ⁺ , where one or more H in NH ₄ ⁺ can be replaced by alkyl radicals,
  R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (H) O groups and optionally non-adjacent -O- and / or -N (H) - and / or tertiary
  contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
  R ^{1 stands} for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (H) O and optionally non-adjacent -O- and / or - N ( H) - and / or tertiary
  contains, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and
  the proportion of AR in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) is at least 20% by weight.

8. Mixture according to claim 7, characterized in that the proportion of A-R the compound of general formula (Ia) at least 15 wt .-%, preferred at least 20% by weight, particularly preferably at least 25% by weight, entirely particularly preferably 35 to 60% by weight, and / or on the compound of  general formula (Ib) at least 25% by weight, in particular 35 to 60% by weight, is. 9. Mixture according to claim 7 or 8, characterized in that L ^a and / or L ^{b represent} a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units. 10. A process for the preparation of compounds of general formula (Ia) and (Ib) according to one of claims 1 to 6, in which polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic acid or maleic anhydride, the reaction product obtained with ethylene oxide, propylene oxide, alkanolamines , Polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols, carbohydrates or sugars are reacted and the free carboxyl group present is optionally converted into the corresponding salt with NH ₃ , an amine or an (earth) alkali metal salt. 11. Use of a compound of general formula (Ia) and / or (Ib) according to one of claims 1 to 6 and / or a mixture according to one of the claims 7 to 9 as a surface-active substance, as an emulsifier, as a wear protection additive, as a lubricity-improving or corrosion-inhibiting additive in Fuels, lubricants, fuel additive and lubricant additive Concentrates or as a corrosion-inhibiting additive in water-containing Liquids. 12. Use according to claim 11, wherein the compound and / or the mixture as Emulsifier in the production of water-in-oil emulsions, especially of Water-in-fuel emulsions, or as a surfactant for industrial and cosmetic Washing and cleaning formulations are used. 13. Fuel, lubricant, fuel additive concentrate, lubricant additive concentrate and water-containing liquid containing one or more Compounds of the general formula (Ia) and / or (Ib) according to one of the Claims 1 to 6 and / or a mixture according to one of Claims 7 to 9, preferably water-in-fuel emulsion containing 60 to 95% by weight Fuel, preferably diesel fuel, 3 to 35% by weight of water and 0.2 to 10% by weight,  preferably 0.5 to 5 wt .-%, one or more compounds of the general formula (Ia) and / or (Ib) according to one of claims 1 to 6 and / or a mixture according to one of claims 7 to 9 as an emulsifier. 14. Washing and cleaning formulation containing one or more compounds of the general formula (Ia) and / or (Ib) according to one of Claims 1 to 6 and / or a mixture according to any one of claims 7 to 9. 15. Emulsion according to claim 13, characterized in that in addition to one or more compounds of the general formula (Ia) and / or (Ib) one or more further emulsifiers, preferably sorbitan monooleate, C ₁₃ - oxo alcohol ethoxylates or alkylphenol ethoxylates, and / or one or more Biocides, preferably NH ₄ NO ₃ and / or glyoxal, particularly preferably glyoxal, are present. 16. A method for producing an emulsion according to claim 13 or 15, characterized characterized in that the respective components are mixed together and in at be emulsified in a known manner, preferably in a mixing nozzle.