WO2002094889A2

WO2002094889A2 - Low-molecular and high-molecular emulsifiers, particularly based on polyisobutylene, and mixtures thereof

Info

Publication number: WO2002094889A2
Application number: PCT/EP2002/005516
Authority: WO
Inventors: Stephan Hüffer; Peter Schwab; Gregor Schürmann; Hans Peter Rath; Helmut Mach; Eckard Schauss
Original assignee: Basf Aktiengesellschaft
Priority date: 2001-05-22
Filing date: 2002-05-17
Publication date: 2002-11-28
Also published as: CA2448033A1; CN1511167A; EP1404726A2; US20040154216A1; AU2002338977A1; JP2004531614A; WO2002094889A3; DE10125158A1

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: La represents a polyisobutylene group having a numerical average molecular weight M¿n? ranging from 300 to 1000; L?b¿ represents a polyisobutylene group having a numerical average molecular weight M¿n? 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 NH¿4?+, whereby in NH¿4?+, 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, NH¿2? 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 NH¿2? or NH3?+¿ groups, one or more H's can be substituted by alkyl radicals, and; R1 represents a linear or branched saturated hydrocarbon radical, which optionally supports one or more substituents selected from the group consisting of OH, NH¿2, 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 NH¿2? or NH3?+¿ groups, one or more H's can be substituted by alkyl radicals, and the proportion of A-R on the compound of general formula (Ib) equals at least 20 wt. %.

Description

Low and high molecular weight emulsifiers, especially those based on polyisobutylene, and their mixtures

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

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

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

For example, US Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and a succinic anhydride substituted with 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 cell-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 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 ^! R ² NR ³ as emulsifiers in water-in-oil emulsions, where R ³ for one

Is an acyl radical of a mono- or polycarboxylic acid, and R ^{1 is derived,} inter alia, from a poly-1-butylene, -2-butylene or -to-butylene or mixtures thereof, and R ^{2 can be} a polyalkylenepolyarnine or a polyalkylenimine radical.

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

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 ₂ o-C5θö hydrocarbon radicals such as polyisobutylenyl groups. In The examples only describe the salts of succinic acids or their monoesters which carry a polyisobutylenyl group with a number average molecular weight of 950 or 1700.

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

For example, US Pat. No. 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula R ¹ (-OR -) _a NH (CO) -R ³ -OH being used as friction-reducing additives, wherein R ^{1 is} for a C] - bis C <so- alkyl radical, R is a C to C ₄ alkylene radical, a is an integer from 1 to 12 and R is Ci to C 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 production and / or product properties. With some compounds, by-products are obtained in the synthesis in different yields, which - if they are not removed - can make it difficult to set a constant viscosity of the emulsifier. Disadvantages can also arise in the production of emulsions: the emulsions often have insufficient stability, so that phase separation occurs during storage. The emulsifiers used must therefore be used in high concentrations to enable the formation of a stable emulsion.

There is therefore a need for compounds which can be used as emulsifiers and which do not have the disadvantages mentioned. Especially in the field of water-in-fuel emulsions, emulsifiers are needed that produce relatively stable emulsions and also enable the most complete and largely residue-free combustion of the fuel.

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

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 ') -,

M ^{+ stands} for H ^{1 "} , an alkali metal ion, 0.5 alkaline earth metal ions or NH, where one or more H in NH ⁺ 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 (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, 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 has one or carries several substituents selected from the group OH, NH ₂ , NH ₃ ⁺ or C (O) H and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and

the proportion of A-R 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 is at lower values such as 5.2 to 15.2% by weight are known per se and are described in GB-A 2,157,744 and US 4,708,753 , However, it does not include the advantageous properties recognized as emulsifiers which occur in the compounds according to the invention with an AR content of ≥ 20% by weight.

The compounds according to the invention can be used both individually and in a mixture as emulsifiers in water-in-oil emulsions. More stable emulsions can be produced 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 general formula (Ia) is at least 25% by weight, 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 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 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or

- The proportion of AR in the compound of general formula (Ib) is at least 25% by weight, 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.

Particularly preferred are 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 radical of a block copolymer of ethylene and 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 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 is used as an emulsifier containing

(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),

(Ia) (Ib)

(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 ^! ) -, M * stands for Ff ^{1 "} , an alkali metal ion, 0.5 alkaline earth metal ions or NELt ^4" , it being possible for one or more H in NHt ^{+ to 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 (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and or tertiary amines, and wherein one or more H in the NH ₂ - or NH ₃ ⁺ groups can 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 (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH ₂ - or NH ₃ ⁺ groups can be replaced by alkyl radicals, and

the proportion of A - R in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) at least 20

% By weight.

Effective emulsifier mixtures are obtained not only when using compounds of the general formula (Ia) with hydrophilic parts of at least 20% by weight, but also when using compounds of the general formula (Ia) with hydrophilic parts of at least 10% by weight.

Mixtures according to the invention which, in addition to at least one compound of the general formula (Ib), are preferred

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 the general formula (Ia) in which L ^{a is} a polyisobutylenyl group with a number-average molecular weight M. _{n is} from 350 to 950, in particular from 350 to 650, and / or the proportion of AR in the connection of the 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.

Mixtures according to the invention which, in addition to at least one compound of the general formula (Ia) -

contain 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) in which L ^{b is} a polyisobutylenyl group with a number average molecular weight M _n of 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% by weight.

The present invention also relates to processes for the preparation of the compounds of the general formula (Ia) or (Ib). Here, polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic anhydride or maleic acid, preferably with maleic anhydride or maleic acid dichloride, particularly preferably with maleic anhydride, is converted to succinic acid derivatives of the general formula (Ha), (Ilb) or (IIc) with one poly, where L ^{a is} a group number average molecular weight M _n of 300 to 1000 and L ^{b is} a polyisobutylenyl group with number average molecular weight M _n of 2000 to 20,000.

(Ha) (Ilb) (IIc)

The reaction is carried out by the processes known to the person skilled in the art and, for example, analogously to the processes for the reaction of polyisobutylenes with maleic anhydride described in German Offenlegungsschriften DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672. 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 (Ha) and (Hb) are then reacted with polar reaction partners ROH or RR NH by processes known to those skilled in the art, where R is a linear or branched saturated hydrocarbon radical which has at least one substituent selected from the group OH, NH ₂ or NH ₃ ⁺ and optionally one or more C (O) H groups and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH ₂ - or NH ⁺ 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 (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and one or more H in the NH - or NH ⁺ groups can be replaced by alkyl radicals.

The alkyl radicals that can replace the H atoms are - - alkyl radicals.

Examples of suitable polar reactants ROH and RR ^ H 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) aminomethane 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 polar reactant is chosen so that the proportion of the hydrophilic radical AR in the compound of general formula (Ia) or (Ib) is at least 20 % By weight, preferably 25% by weight, particularly preferably 35 to 60% by weight. Compounds of the general formula (Ia) in which the hydrophilic content is 10 to 20% by weight can also be prepared by the processes described. The conversion ratio of the substituted succinic acid derivatives (Ha), (üb) or (IIc) to 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 is selected in accordance with the desired chain length of the hydrophilic radical AR.

Compounds of the general formula (Ia) or (Ib) in which A = -O- and R are a monovalent radical of an oligomer or polymer of ethylene and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide can be used obtained both by reacting polyethylene glycol, polypropylene glycol or their (block) copolymers with the substituted succinic acid derivatives (Ha), (Ilb) or (IIc), and also by reacting ethylene oxide and or propylene oxide with the substituted succinic acid derivatives (Ha), (Ilb) or (IIc).

By reacting the substituted succinic acid derivatives (Ha), (Ilb) or (IIc) with the polar reaction partners 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 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 semiesters and half amides can then be reacted with NH ₃ , amines, alkali metal or alkaline earth metal salts to give the corresponding A 1, alkali metal or alkaline earth metal salts. These salts are compounds of the general formula (Ia) or (Ib) in which M * ^"is an alkali metal ion, 0.5 alkaline earth metal ion or NEU, where one or more H in NELi * can be replaced by alkyl radicals 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 by one or more hydroxyl groups.Examples of suitable alkyl amines 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).

To prepare 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 70 mol%, preferably ≥ 80 mol%, particularly preferably ≥ 85 mol%.

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 pers 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, from BASF AG under the trade name Glissopal®, 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, oligoalcohols, polyols and polyalkylene glycols which can be used for the preparation of the compounds according to the invention are described in WO 00/15740.

Examples of alkanolamines are monoethanolamine, diethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl- 1,3-propanediol, N- (2-hydroxypropyl) -N '- (2-aminoethyl) piperazine, tris (hydroxymethyl) amino-methane, 2-amino-1-butanol, ß- (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) -l, 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 tetaethylene 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 d-Cβ-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 polypentylene polyamines; see also "Ethylene Amines" in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Volume 7, pp. 22-37, Interscience Publishers, New York 1965.

Examples of suitable oligoalcohols and polyols are 1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol, 1,2-cyclohexanediol, (mono-, di-) - pentaerythritol, 1.7 - and 2,4- heptanediol, 1,2,3-, 1,2,4-, 1,2,5- and 2,3, 4-hexanetriol, 1,2,3- and 1,2,4- Butanetriol, 2,2,6,6-tetrakis (hydroxymethyl) cyclohexanol, 1,10-decanediol, 2-hydroxymethyl-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 preferred 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 "of 600, Pluriol® E 4000 with an M" of 4000 and Pluriol® E 5000 with an M _n of 5000. Polyethylene-polypropylene glycol block copolymers are available, for example, from BASF AG under the trade name Pluronic® PE, such as Pluronic® PE 3500 with an M _n of 1900 and an ethylene oxide content of 50% by weight. ,

If the compounds according to the invention and or the mixtures according to the invention are used in oil-in-water emulsions, stable vesicles can be produced. This can be done, for example, by the action of ultrasound. The compounds of the invention and / or the mixtures of the invention can also be used in a variety of ways, e.g. B. as additives in fuels and lubricants, as a corrosion-inhibiting additive in water-containing liquids and as dispersants for inorganic and organic solid dispersions. The compounds according to the invention and / or the mixtures according to the invention can also be used as surfactants for washing and cleaning formulations. The high-molecular compounds of the general formula (Ib) which contain a monovalent residue of a polyethylene glycol as a hydrophilic block are particularly suitable for stabilizing inorganic and organic solid dispersions.

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

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

In general, it is not necessary to purify the compounds according to the invention and their intermediates; only in certain applications, for example when using these compounds as emulsifiers for water-in-oil emulsions in the cosmetics or pharmaceutical field, may purification be necessary.

The use of compounds according to the invention and / or mixtures according to the invention as emulsifiers in the production of water-in-oil emulsions is just as much a subject of the invention as the water-in-oil emulsions themselves. Water-in-oil emulsions according to the invention generally contain 95 up to 60% by weight of oil, 3 to 35% by weight of 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 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. By adding one or more C ₁ -C ₄ alcohols and / or monoethylene glycol, for example, the temperature range in which the emulsion is stable can be broadened.

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

The water-in-fuel emulsions according to the present invention can have further components in addition to the components mentioned above. These are, for example, other 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 of ethylene oxide and propylene oxide, such as the Pluronic® types from BASF AG. Sorbitan monooleate, C ₁₃ oxo alcohol ethoxylates and alkylphenol ethoxylates, for example octyl and nonylphenol ethoxylates, are preferably used as further emulsifiers.

A combination of one or more of the above-mentioned further emulsifiers together with the compounds according to the invention and / or mixtures thereof is preferably used for the water-in-fuel emulsions according to the invention.

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

To prepare the water-in-oil emulsions according to the invention, the compounds and / or mixtures according to the invention are mixed with the oil, the water and the further, optionally usable components and emulsified in a manner known per se. For example, the emulsification can be carried out in a rotor mixer, by means of a mixing nozzle or by an ultrasound probe. Particularly good results were achieved when a mixing nozzle of the type used as disclosed in German application, file number: 198 56 604 by the applicant on December 8, 1998 was used. Water-in-oil emulsions for the cosmetics sector can be produced as well as water-in-fuel emulsions.

In addition to their surface-active, surface-active and emulsifying properties, the compounds and / or mixtures according to the invention also have a lubricity-improving and corrosion-inhibiting effect. They also improve the wear protection behavior of liquids. The compounds and / or mixtures according to the invention are therefore used as additives for lubricants, fuels and water-containing liquids such as coolant liquids or drilling and cutting liquids. This use is also the subject of the present invention. The compounds and / or mixtures according to the invention can be added directly to the fuels and lubricants — together with other components. Alternatively, the compounds according to the invention and or mixtures according to the invention can first be mixed with other components to give fuel or lubricant additive concentrates. These fuel or lubricant additive concentrates according to the invention can be added to the fuels or lubricants undiluted or diluted with one or more solvents or carrier oils. The addition in dilute form is preferred.

The fuels, lubricants, fuel additive and lubricant additive concentrates, and also water-containing liquids which contain the compounds and / or mixtures according to the invention are likewise 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 a mixture according to the invention in an amount of 10 to 5000 ppm, preferably in an amount of 20 to 2000 ppm, based on the total amount.

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

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

Typical components for fuels or fuel additive concentrates are, for example, additives with detergent action, as described in the applicant's German application, file number 100 36 956.1, dated July 28, 2000 (page 14 ff.), In the applicant's German application, file number 100 03 105.6, dated 25.1.2000 and in the PCT application of the applicant with the file number PCT / EP / 01/00496. The additives mentioned there and other fuel additives described there with polar Generations are part of the present application and are incorporated by reference.

The fuels and fuel additive concentrates according to the invention can also contain fuel additives as described, for example, in European patent applications EP-A 0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810, 0 568 873, German patent applications DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270, 196 14 349, and WO-A 96/03479.

Other common components are, for example, other corrosion-inhibiting additives, antioxidants, stabilizers, antistatic agents, organometallic compounds, wear protection additives, dyes and cetane number improvers, flow improvers, biocides such as glutardialdehyde or glyoxal. The biocides are usually used in an amount of 0.01 to 3% by weight, based on the total weight of the concentrate.

Examples of further corrosion-inhibiting additives are those based on ammonium salts of organic carboxylic acids, which tend to form films, or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection.

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

Examples of organometallic compounds are ferrocene or methylcyclopentadienylmanganese tricarbonyl.

Examples of cetane number improvers are organic C -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. 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

the fuels and lubricants themselves as well as 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 "from 400 to 1800. Polyethylene oxides, polypropylene oxides, polybutene oxides and mixtures thereof are also suitable carrier oils. Further suitable carrier oils and carrier oil mixtures are described, for example, in the publications DE-A 38 38 918, DE-A 38 26 608, DE-A 41 42241, DE-A 43 09074, US 4,877,416 and EP-A 0452 328.

Water-containing liquids according to the invention contain the compounds and / or mixtures according to the invention, if appropriate in combination with other customary corrosion-inhibiting additives, generally in a proportion of about 1 to 10% by weight, based on the total amount.

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

embodiments

Example 1: Preparation of the compounds of the general formulas (Ia) and (Tb)

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

Glissopal® from BASF AG with a number average molecular weight M _n of 380 to 8400 and a proportion of vinylidene end groups of> 70 was used as polyisobutylene

Mol .-%, a polydispersity M _w / M _n in the range of 1.15 to 1.8 and one Polymer scaffold structure with more than 85% isobutylene units used. This polyisobutylene served as a starting material for the synthesis of succinic anhydride (PIBSA) 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.

Clariant, commercially available under the name Ambossol®, was used as the ion exchanger.

The 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.

The compounds obtained were characterized via the acid number, the OH number, the viscosity and / or the IR spectra. The OH number was determined using solvent when using high-boiling solvents, i. H. that the OH number of the compounds in the respective solvent was measured and then extrapolated to the pure substance. In the case of low-boiling solvents such as heptane, the solvent was removed by distillation and the OH number was determined from the pure substance.

The viscosities were always determined in accordance with DLN 51562.

Table 1: Composition of the compounds of the general formula (Ia) or (Ib)

Preparation of compound A:

An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 250 g PIBSA 550 and heated to 90 ° C. 67 g of diethanolamine are metered in via a dropping funnel 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 21 four-necked flask with stirrer, distillation bridge and thermocouple is filled with 525 g PIBSA 550, 650 g Solvesso® 150 and 175 g trihydroxymethylaminomethane (TRIS). The mixture is gradually heated to 130 ° C or 170 ° C. Released water is removed using a stream of nitrogen; the reaction time is 3 hours. The OH number was determined to be 250 when adjusted for solvent. Preparation of compound C:

An 11 four-necked flask with stirrer, distillation bridge and thermocouple is filled with 310 g PIBSA 750 and 60 g D-sorbitol. The mixture is gradually heated to 160 ° C or 220 ° C. Released water is removed using a stream of nitrogen; after 3 hours at 220 ° C, diluted with 200 g of Mihagol and filtered hot. A yellow, viscous product solution (65%) is obtained.

Preparation of compound D:

A 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 350 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum. A solution of 650 g of PIBSA 380 in 350 g of heptane is metered into a dropping funnel at 80 ° C. in the course of 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). 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 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum. 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 21 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. About one In the dropping funnel, a solution of 790 g of PIBSA 1000 in 450 g of heptane is metered in at 80 ° C. in the course of 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). 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 connection G:

An 11 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:

An 11 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 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 / s; 100 ° C.

Preparation of compound L:

An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 75 g of a 45% methanolic solution of choline from Fluka and 150 g of Mihagol. Methanol is then removed at 50 ° C and reduced pressure (50 mbar) (45 minutes). 200 g of PIBSA 550 are added to this suspension and the mixture is heated to 90 ° C. in the course of 15 minutes. After 60 minutes, the temperature is raised to 170 ° C. and the mixture is stirred for a further two hours. The brown reaction product is filtered at 100 ° C.

Preparation of compound M for comparative example 2:

An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g PIBSA 2300, 200 g PIBSA 1000 and 200 g Mihagol and heated to 95 ° C. 17.2 g of ethylene glycol are metered in at 95.degree. The mixture is heated to 130 ° C. and stirred at this temperature for three hours. The brown reaction product is filtered at 100 ° C.

The emulsifier of comparative example 2 was produced according to the principle of WO 00/15740 according to 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 an AR of 35.3%, while in compound N the hydrophilic fraction AR is 15.4%.)

A 21 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: Preparation of the water-in-fuel emulsions

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

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

Table 2 (see next page): Composition of the emulsions

* Either glyoxal or glutaraldehyde was used as the biocide.

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

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

The size of the water drops was physically determined by laser diffraction (X3, 2 values) using a Malvem Mastersizer 2000 from Malvem Instruments GmbH. The measurement method is described, for example, in Terence Allen, Particle Size Measurement, Volume 1, 5 ^ft Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999. Depending on the actual size distribution, there are other methods besides laser light diffraction such as: 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 can be seen in Table 3, the emulsions using the compounds according to the invention and also the mixtures according to the invention sometimes have significantly smaller drop sizes than the comparison emulsions. The fact that the drop size is really a measure of the stability of the emulsion at room temperature is shown by the stability values determined by storage tests. The emulsions with larger droplet sizes also have poorer storage stability.

Table 3: Drop size and stability of the water-in-fuel emulsions

12 weeks; ** 1 week

The stability of the emulsions was checked in a static storage test at 20 ° C (for 12 weeks) and additionally under changing temperatures (-20 ° C and 70 ° C, each for 1 week). For this purpose, the emulsion was filled into a scaled 100 ml standing cylinder and its quality was assessed visually in accordance with the specified conditions. Compared to the use of emulsifiers from the prior art (comparative examples), a partially significant improvement in the storage stability can be observed using the emulsifiers according to the invention and their mixtures. The storage tests at -20 ° C were then assessed at room temperature. After thawing, the emulsion according to Example 2 is comparatively homogeneous even without the addition of anti-freeze (e.g. monoethylene glycol). Otherwise, phase separation, a so-called "breaking" of the emulsion, took place after or even when heated.

A comparison of the quality of the emulsions according to the invention with an emulsion according to WO 00/15740 (Example C-1, p. 34, Comparative Example 2) proves that a combination of a low molecular weight component and a higher molecular weight component to form a correspondingly bridged compound results in a significantly worse one Emulsifier performs as a mixture according to the invention of the isolated compounds.

Example 4: Use of the compounds of the general formula (I) according to the invention as rust protection and wear protection additives

A 20 x 40 mm sheet of iron is blasted with 40 μm glass beads and then - based on ASTM D-665 - immersed in the emulsions prepared 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;

-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 4, when using the compounds according to the invention as corrosion-inhibiting additives, in some cases only slight rust formation was observed. In contrast to this, rust formation occurred on more than 50% of the surface of the test sheet when using C ₃ -oxoalcohol ethoxylate.

Example 5: Use of the compounds of the general formula (I) according to the invention in fuels and their wear protection behavior The connections listed in the table were solved in an unadditized diesel fuel (Miro, Karlsruhe). The concentration of additive in the diesel fuel was 75 ppm. The wear protection behavior was assessed using the HFRR test (High Frequency Roller Rig Test), which was carried out in accordance with ISO 12156-1. The length of the resulting grooves was measured and used as a measure of wear. The shorter the scoring, the better the wear protection of the additive added. Unaddivated diesel fuel was used for comparison. As can be seen from Table 4, the compounds according to the invention protected against wear.

Table 4:

Claims

claims

Compound of the general formula (Ia) and (Ib)

(Ia) (Ib)

-A- stands for -O-, -N (H) - or -N (R ^J ) -,

M * stands for H ⁺ , an alkali metal honey, 0.5 alkaline earth metal ions or NH, where one or more H in NE ⁺ can 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 (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH ₂ - or NH ₃ ⁺ groups can 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 ⁺ or C (O) H and optionally one or more non-adjacent -O- and / or secondary amines and / or contains tertiary amines, and wherein one or more H in the NH ₂ or NH ₃ groups can 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 "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 spoke 1 or 2, characterized in that L ^a and L ^{b represent} a polyisobutylenyl group having 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 consists of at least 80 wt .-%

Isobutylene units is built up.

5. A compound according to any one of claims 1 to 4, characterized in that the proportion of A-R in the compound of general formula (Ia) and (Ib) is at least 25% by weight, in particular 35 to 60% by weight.

6. A compound according to any one of claims 1 to 5, characterized in that A = - O- and R is a monovalent radical of an oligomer or polymer of ethylene oxide and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide.

7. Containing mixture

(Ia) (Ib)

-A- stands for -O-, -N (H) - or -N (R ') -,

M ^{1 "stands} for ϊt, an alkali metal ion, 0.5 alkaline earth metal ions or NH ₄ ^1" , where in t ^" one or more H can be replaced by alkyl radicals,

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 (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein in the NH ₂ - or NH ₃ ⁺ groups one or more H may be replaced by alkyl radicals, and

the proportion of A-R in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) at least 20

% By weight.

8. Mixture according to claim 7, characterized in that the proportion of AR in the compound of the 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 wt .-%, and / or on the compound of general formula (Ib) is at least 25% by weight, in particular 35 to 60% by weight.

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 any one of claims 1 to 6, in which polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic acid or

Maleic anhydride reacted, the reaction product obtained is reacted with ethylene oxide, propylene oxide, alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols, carbohydrates or sugars and the free carboxyl group present, if appropriate, with NH ₃ , an amine or an (earth) alkali metal salt in the corresponding Salt is transferred.

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 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 an emulsifier in the production of water-in-oil emulsions, in particular water-in-fuel emulsions, or as a surfactant for industrial and cosmetic washing and cleaning formulations is 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 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% by weight, of 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 one of claims 7 to 9.

15. Emulsion according spoke 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 NFL _f NO ₃ and / or glyoxal, particularly preferably glyoxal, are present.

16. A method for producing an emulsion according to spoke 13 or 15, characterized in that the respective components are mixed together and emulsified in a manner known per se, preferably in a mixing nozzle.