CN1511167A - Low and high molecular weight emulsifiers, especially based on 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

Lower molecular weight and high-molecular weight emulsifying agent, especially based on the emulsifying agent of polyisobutene and their mixture

The present invention relates to lower molecular weight and high-molecular weight compound, especially based on the compound of polyisobutene, and their mixture, they are suitable as the emulsifying agent of water-in-oil emulsion, relate to the preparation method and the emulsion itself of this compounds.

The invention still further relates to that this compounds acts as a fuel and lubricant additive and, and relate to fuel, lubricant, fuel additive concentrate and the slip additive enriched material and liquid, aqueous that contains this novel cpd as the purposes of corrosion inhibiting additive in liquid, aqueous.

Various types of compounds with emulsifying property are open in the prior art.Especially, the derivative of the succinyl oxide of polyisobutenyl replacement is used for various application.

For example, US-A 4,225, and 447 have described the water-in-oil type emulsion as lubricant, and it contains succinyl oxide (the number-average molecular weight M that preferably has 300-3000 gram/mole that thiazolinyl (for example polyisobutenyl) replaces _n), the succinic diamide of an alkali metal salt of the succsinic acid of alkenyl substituted or alkaline earth salt or alkenyl substituted is as emulsifying agent, when needed, be used in combination with the salt of resinous acid.

EP-A 0 156 572 has described the purposes that is used to prepare water-in-oil-type or emulsion oil-in-water based on the anionic surface active substances of the succinic acid derivative of polyisobutenyl replacement, and this material preferably has the number-average molecular weight M of 400-5000 gram/mole _nAnd has an anionic group.Suitable anionic group is phosphate radical, phosphonate radical, sulfate radical, sulfonate radical and carboxymethyl.

In the application number of on January 25th, 2000 application is that the applicant of 100 03 105.6 German patent application has been described the act as a fuel purposes of the emulsifying agent in the water-in type emulsion of alkoxylate polyisobutene.These alkoxylate polyisobutene can be by general formula R-(CH ₂) _n-(O-A) _m-OH describes.Here, R is the polyisobutene with weight-average molecular weight of 300-2300, preferred 500-2000.A is the alkylidene group with 2-8 carbon atom.M is the number of 1-200, and it makes the alkoxylate polyisobutene contain 0.2-1.5 alkylene oxide unit through selecting, and preferred 0.5 alkylene oxide unit is with each C ₄The unit meter; N is 0 and 1.

The application number of on July 28th, 2000 application is that the applicant of 100 36 956.1 German patent application has especially been described general formula R ¹R ²NR ³Acid amides as the purposes of the emulsifying agent in the water-in-oil emulsion, wherein R ³Be monocarboxylic acid or polycarboxylic acyl group, R ¹Especially derive autohemagglutination 1-butylene, poly-2-butylene or polyisobutene or their mixture, R ²Can be polyalkylenepolyamines or polyalkylene imine group.

WO 00/15740 has described the water-in-fuel emulsion, it contains two kinds of succinic acid derivatives as emulsifying agent, for example alkanolamine, polyamines or polyvalent alcohol connect these two kinds of derivatives via linking agent, and by for example polyisobutenyl replacement of alkyl, in one embodiment, a kind of succinic acid derivative contains the polyisobutenyl of 8-25 carbon atom, and another kind of succinic acid derivative contains the polyisobutenyl of 50-400 carbon atom.

GB-A 2,157, and 744 disclose drilling fluid, and it contains the grafting or the segmented copolymer of poly carboxylic acid and polyoxyethylene glycol simultaneously, and contain succinyl oxide (the number-average molecular weight M that preferably has 400-5000 that replaces from polyisobutenyl _n) and the compound that makes of polyvalent alcohol, preferred polyamines, hydroxycarboxylic acid or amino alcohol.

US4,708,753 have described the water-in-fuel emulsion, and it contains the amine salt of single salt of succsinic acid and amine or disalt or monomester succinate as emulsifying agent.These salt are by alkanolamine, polyamines, low polyalcohols or polyvalent alcohol and by C ₂₀-C ₅₀₀The succinyl oxide that alkyl (for example polyisobutenyl) replaces reacts and forms.In example, only described and had the succsinic acid of polyisobutenyl that number-average molecular weight is 950-1700 or those salt of its monoesters.The antifriction additive of fuel and lubricant and emulsifying agent is disclosed in the prior art.

Therefore, US5,858,029 have described antifriction liniment, the especially general formula R of fuel and lubricant ¹(O (R ²)-) _aNH (CO)-R ³The compound of-OH, wherein R ¹Be C ₁-to C ₆₀-alkyl, R ²Be C ₁-to C ₄-alkylidene group, a are the integers of 1-12, R ³Be C ₁-to C ₄The alkylidene group of-alkylidene group or replacement or cycloalkylidene, this compound is as the antifriction liniment.In addition, the succinimide that polyisobutenyl replaces can be used as dispersion agent and exists, and polyalkenes amine such as polyisobutene amine can be used as tensio-active agent and exist.

Disclosed in the prior art above-claimed cpd has the various shortcomings with regard to preparation and/or product performance.For some compounds, in synthetic, can generate the by product of different yields, unless they are removed otherwise the feasible constant viscosity that is difficult to obtain this emulsifying agent.Shortcoming also may reside in the preparation of emulsion: the stability of this emulsion is usually not enough, so be separated between the shelf lives.Therefore, in order to form stable emulsion, employed emulsifying agent must use with high density.

Therefore needing can be as emulsifying agent and the compound that does not have this type of shortcoming.Especially in the field of water-in-fuel emulsion, need such emulsifying agent, they can form more stable emulsion and allow fuel combustion as far as possible completely in addition and be substantially free of residue.

The purpose of this invention is to provide can be as other compound of the emulsifying agent in the water-in-oil emulsion.

We have found that this purpose can realize by general formula (Ia) and compound (Ib),

L wherein ^aBe that number-average molecular weight Mn is the polyisobutenyl of 300-1000,

L ^bBe that number-average molecular weight Mn is the polyisobutenyl of 2000-20000,

-A-is-O-,-N (H)-or-N (R ¹)-,

M ⁺Be H ⁺, alkalimetal ion, 0.5 alkaline-earth metal ions or NH ₄ ⁺, NH wherein ₄ ⁺In one or more H can be replaced by alkyl,

R is the saturated hydrocarbyl of straight or branched, and it has at least one and is selected from OH, NH ₂And NH ₃ ⁺Substituting group and contain one or more C (O) group when needed and contain when needed one or more non-conterminous-O-, and/or secondary amine and/or tertiary amine are wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl and

R ¹Be the saturated hydrocarbyl of straight or branched, when needed, it has one or more OH of being selected from, NH ₂, NH ₃ ⁺And the substituting group of C (O) H and contain when needed one or more non-conterminous-O-, and/or secondary amine and/or tertiary amine are wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl and

In general formula (Ia) or compound (Ib), the ratio of A-R is at least 20 weight %.

Wherein formula (Ia) compound of hydrophilic radical A-R ratio low (for example 5.2-15.2 weight %) is that itself is known, is described among GB-A 2157744 and the US4708753.But, wherein do not recognize the advantageous property that under the new compound situation of A-R ratio 〉=20 weight %, occurs as emulsifying agent.

Described novel cpd can use separately, also can be used as emulsifying agent in water-in-oil emulsion with the form of mixture.Can prepare emulsion more stable when using conventional emulsifier like this.Particularly, the compound of formula (Ib) can be used as two block emulsifying agents, connects via linking agent, wherein oleophylic block L ^aOr L ^bBe connected on the linking agent succsinic acid hydrophilic block R or R by the covalency C-C ¹Be connected on the described linking agent by ester or amido linkage.

Preferred formula (Ia) compound is such, wherein:

-L ^aBe that number-average molecular weight Mn is the polyisobutenyl of 350-950, particularly 350-650, and/or

-L ^aBe polymolecularity≤3.0, be preferably the polyisobutenyl of 1.1-2.5, preferred especially 1.1-2.0, and/or

-in the compound of general formula (Ia), the ratio of A-R is at least 25 weight %, particularly 35-60 weight %, and/or

-R is by [CH ₂-CH ₂-X], [CH (CH ₃)-CH ₂-X] and/or [CH ₂-CH (CH ₃)-X] the unit composition, wherein X is O or NH.

Preferred formula (Ib) compound is such, wherein:

-L ^bBe that number-average molecular weight Mn is the polyisobutenyl of 2000-12000, particularly 2300-5000, and/or

-L ^bBe polymolecularity≤3.0, be preferably the polyisobutenyl of 1.1-2.5, preferred especially 1.1-2.0, and/or

-in the compound of general formula (Ib), the ratio of A-R is at least 25 weight %, particularly 35-60 weight %, and/or

-R is by [CH ₂-CH ₂-X], [CH (CH ₃)-CH ₂-X] and/or [CH ₂-CH (CH ₃)-X] the unit composition, wherein X is O or NH.

Particularly preferred general formula (Ia) or (Ib) compound be such, wherein A is-O-, and R is the oligopolymer of oxyethane and/or propylene oxide or the monoradical of polymkeric substance, perhaps R is the monoradical of the segmented copolymer of oxyethane and propylene oxide.

Especially effectively emulsifying agent is such general formula (Ia) compound, wherein L ^aBe that number-average molecular weight Mn is the polyisobutenyl of 350-950, particularly 350-650, this polyisobutenyl has when needed≤3.0, be preferably 1.1-2.5, preferred especially 1.1-2.0 polymolecularity.Have been found that if used emulsifying agent is the mixture that contains following component, then can reduce the total amount that is used to prepare the required emulsifying agent of stable emulsion,

(a) be no more than at least a formula (Ia) compound of 99 weight %, preferred 98-80 weight %, preferred especially 97-85 weight %,

(b) at least a formula (Ib) compound of at least 1 weight %, preferred 2-20 weight %, preferred especially 3-15 weight %,

L wherein ^aBe that number-average molecular weight Mn is the polyisobutenyl of 300-1000, L ^bBe that number-average molecular weight Mn is the polyisobutenyl of 2000-20000,

-A-is-O-,-N (H)-or-N (R ¹)-,

M ⁺Be H ⁺, alkalimetal ion, 0.5 alkaline-earth metal ions or NH ₄ ⁺, NH wherein ₄ ⁺In one or more H can be replaced by alkyl,

R is the saturated hydrocarbyl of straight or branched, and it has at least one and is selected from OH, NH ₂And NH ₃ ⁺Substituting group and contain one or more C (O) H group when needed and contain when needed one or more non-conterminous-O-, and/or secondary amine and/or tertiary amine are wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl and

R ¹Be the saturated hydrocarbyl of straight or branched, when needed, it has one or more OH of being selected from, NH ₂, NH ₃ ⁺And the substituting group of C (O) H and contain when needed one or more non-conterminous-O-, and/or secondary amine and/or tertiary amine are wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl and

In the compound of general formula (Ia), the ratio of A-R is at least 10 weight % and in general formula (Ib) compound, and the ratio of A-R is at least 20 weight %.

Effectively emulsifier mixture not only uses formula (Ia) compound with at least 20 weight % hydrophilic segments, and uses formula (Ia) compound with at least 10 weight % hydrophilic segments to obtain.

Preferred model mixture is such, and it also contains at least a formula (Ia) compound that is no more than 99 weight %, preferred 98-80 weight %, preferred especially 97-85 weight %, wherein L except containing at least a formula (Ib) compound ^aBe that number-average molecular weight Mn is the polyisobutenyl of 350-950, particularly 350-650, and/or in general formula (Ia) compound, the ratio of A-R is at least 15 weight %, preferably at least 20 weight %, especially preferably at least 25 weight %, very particularly preferably 35-60 weight %.

Other preferred model mixture is such, and it also contains at least a formula (Ib) compound of at least 1 weight %, preferred 2-20 weight %, preferred especially 3-15 weight %, wherein L except containing at least a formula (Ia) compound ^bBe that number-average molecular weight Mn is the polyisobutenyl of 2000-12000, particularly 2300-5000, and/or in general formula (Ib) compound, the ratio of A-R is at least 25 weight %, particularly 35-60 weight %.

The invention still further relates to a kind of preparation formula (Ia) or (Ib) method of compound.Wherein, polyisobutene and rich horse diacid chloride, fumaric acid, Malaysia diacid chloride, maleic anhydride or toxilic acid reaction, preferably with maleic anhydride or the reaction of Malaysia diacid chloride, preferred especially and maleic anhydride reaction, obtain formula (IIa), (IIb) or succinic acid derivative (IIc)

L wherein ^aBe that number-average molecular weight Mn is the polyisobutenyl of 300-1000, L ^bBe that number-average molecular weight Mn is the polyisobutenyl of 2000-20000.

This reaction is undertaken by well known to a person skilled in the art method, for example with DE-A 195 19042, DE-A 43 19 671 and DE-A 43 19 672 in polyisobutene and maleic anhydride response class seemingly.

The number-average molecular weight Mn of gained succinyl oxide derivative (being replaced by polyisobutenyl) can be characterized by saponification value [mg KOH/g material].

The succinic acid derivative of formula (IIa) and replacement (IIb) is then according to well known to a person skilled in the art method and polar reaction agent ROH or RR ¹The NH reaction, wherein R is the straight or branched saturated hydrocarbyl, it has at least one and is selected from OH, NH ₂And NH ₃ ⁺Substituting group and contain one or more C (O) H group when needed and contain when needed one or more non-conterminous-O-and/or secondary amine and/or tertiary amine, wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl and

R ¹Be the saturated hydrocarbyl of straight or branched, when needed, it has one or more OH of being selected from, NH ₂, NH ₃ ⁺And the substituting group of C (O) H and contain when needed one or more non-conterminous-O-and/or secondary amine and/or tertiary amine, wherein at NH ₂-or NH ₃ ⁺One or more H in the group can be replaced by alkyl.

Replacing the alkyl of H atom can be C ₁-C ₄Alkyl.

Suitable polar reaction agent ROH and RR ¹The example of NH is alkanolamine, polyamines, low polyalcohols, polyvalent alcohol, oligo alkylene glycols, polyalkylene glycol and carbohydrate and carbohydrate.Other polar reaction agent can be oxyethane and/or propylene oxide.It is preferred reacting with polyoxyethylene glycol, polypropylene glycol, its (block) multipolymer, oxyethane or propylene oxide.For preparation low-molecular-weight formula (Ia) compound, and the reaction between alkanolamine (for example two-or trolamine, three (methylol) aminomethane and salt thereof), low polyalcohols (for example sorbyl alcohol and tetramethylolmethane) or carbohydrate and the carbohydrate also is preferred.And the reaction between three (methylol) aminomethane, choline, carbohydrate and the polyoxyethylene glycol is to be particularly preferred for preparation formula (Ia) compound.

Select the amount of polar reaction agent, make that in general formula (Ia) or compound (Ib) ratio of hydrophilic radical A-R is at least 20 weight %, preferably at least 25 weight %, especially preferably 35-60 weight %.Wherein hydrophilic radical formula (Ia) compound that accounts for 10-20 weight % also can be by described method preparation.In reaction, the succinic acid derivative (IIa) that replaces, (IIb) or (IIc) with alkanolamine, polyamines, hang down the ratio normally 1 between polyalcohols, polyvalent alcohol, oligo alkylene glycols or the polyalkylene glycol: (0.75-2), preferred 1: (0.8-1.2), preferred especially 1: 1.In the reaction of oxyethane and/or propylene oxide, select the amount of oxyethane and/or propylene oxide according to the chain length of required hydrophilic radical A-R.

Wherein A be-O-and R be the monoradical of the oligopolymer of oxyethane and/or propylene oxide or polymkeric substance or ethylene oxide/propylene oxide segmented copolymer monoradical formula (Ia) or (Ib) succinic acid derivative (IIa) that compound can be by making polyoxyethylene glycol, polypropylene glycol or its (block) multipolymer and replacement, (IIb) or (IIc) reaction obtain and the succinic acid derivative (IIa) by making oxyethane and/or propylene oxide and replacement, (IIb) or (IIc) react and obtain.

Succinic acid derivative (IIa) by making replacement, (IIb) or (IIc) and described polar reaction agent reaction have obtained monomester succinate or mono succinate acid amides.When using alkanolamine, hydroxyl and/or amino react, thereby obtain the mixture of monomester succinate and mono succinate acid amides usually.If use Malaysia diacid chloride or rich horse diacid chloride as raw material, then C (O) the Cl group that still exists after described reaction is hydrolyzed into CO ₂The H group.The free CO that in monomester succinate and mono succinate acid amides, exists ₂The H group then with NH ₃, amine or an alkali metal salt or alkaline-earth metal reactant salt, obtain corresponding amine, an alkali metal salt or alkaline earth salt.These salt are formula (Ia) or compound (Ib), wherein M ⁺Be H ⁺, alkalimetal ion, 0.5 alkaline-earth metal ions or NH ₄ ⁺, NH wherein ₄ ⁺In one or more H can be replaced by alkyl.Be applicable to that salifiable amine is to have straight chain C ₁-C ₄Alkyl or side chain C ₃-C ₆The primary amine of alkyl, secondary amine and tertiary amine.These alkyl also can be replaced by one or more hydroxyls.Suitable alkylamine is for example diethylamide, diisopropylamine, Trimethylamine, single-, two-and three-thanomin and three (methylol) aminomethane.

In general, number-average molecular weight Mn is 300-1000, preferred 350-950, especially preferably the polyisobutene of 350-650 is used for the compound of preparation formula (Ia).

In general, number-average molecular weight Mn is 2000-20000, preferred 2000-12000, especially preferably the polyisobutene of 2300-5000 is used for the compound of preparation formula (Ib).

In the polyisobutene in number-average molecular weight Mn is in described scope, those with high vinylidene content are preferred uses.In the context of the present invention, this is understood that to refer to 〉=70 moles of %, preferred 〉=80 moles %, the vinylidene of preferred 〉=85 moles of % especially.

Having number-average molecular weight Mn in above-mentioned scope, high vinylidene content and those polyisobutene of homogeneous polymer skeleton structure is preferred especially uses.In this article, they are interpreted as referring to those polyisobutene of being made up of at least 80 weight %, preferred at least 90 weight %, preferred especially at least 95 weight % iso-butylene unit.

Have number-average molecular weight Mn in this scope, high vinylidene content and uniformly the polyisobutene of skeleton structure and polymolecularity≤3.0, preferred 1.1-2.5, preferred especially 1.1-2.0 be particularly preferred.Polymolecularity is understood that to refer to the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn.

Have the number-average molecular weight Mn in this scope and form by the iso-butylene unit basically and polyisobutene with high vinylidene content for example can obtain from BASF AG with trade(brand)name Glissopal , as Mn is 1000 Glissopal  1000, and Mn is that 550 Glissopal  V33 and Mn are 2300 Glissopal  2300.

Be applicable to that alkanolamine, the polyamines for preparing novel cpd, the example that hangs down polyalcohols, polyvalent alcohol and polyalkylene glycol are described among the WO 00/15740.

The example of alkanolamine is a monoethanolamine, diethanolamine, 2-amino-1-butanols, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol, N-(2-hydroxypropyl)-N '-(2-aminoethyl) piperazine, three (methylol) aminomethane, 2-amino-1-butanols, β-(2-hydroxyl-oxethyl) ethylamine, glycosamine, glucosamine, 4-amino-3-hydroxy-3-methyl-1-butylene, N-(3-aminopropyl)-4-(2-hydroxyethyl) piperidines, 2-amino-6-methyl-6 enanthol, 5-amino-1-amylalcohol, N-(2-hydroxyethyl)-1, the 3-diaminopropanes, 1,3-diamino-2-hydroxy propane, N-(2-hydroxyethyl)-quadrol, N, N-two (2-hydroxyethyl) quadrol, N-(2-hydroxyethoxy ethyl) quadrol, 1-(2-hydroxyethyl) piperazine, the diethylenetriamine that single hydroxypropyl replaces, the tetren that dihydroxypropyl replaces, and N-(3-hydroxyl butyl)-four ethylene diamines.

Also can use the salt of described alkanolamine.In these salt, one or more H atoms that are connected with the N atom can be by straight chain C ₁-C ₆Alkyl or side chain C ₃-C ₆Alkyl replaces.As an example, can mention choline.

Suitable polyamines is a polyalkylenepolyamines for example, for example multi-methylene polyamine, polyethylene polyamine, many propylidene polyamines, many butylidenes polyamines and many pentylidene polyamines, referring to Ethylene Amines inKirk Othmer ' s Encyclopedia of Chemical Technology, the 2nd edition, the 7th volume, the 22-37 page or leaf, Interscience Publishers, New York 1965.

Suitable oligomeric pure and mild polyvalent alcohol is for example 1,2-butyleneglycol, 2,3-dimethyl-2,3-butyleneglycol, 2,3-hexylene glycol, 1,2-cyclohexanediol, (single-, two-) tetramethylolmethane, 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, the 4-trihydroxybutane, 2,2,6,6-four (methylol) hexalin, decamethylene-glycol, 2-methylol-2-methyl isophthalic acid, ammediol, 2-methylol-2-ethyl-1, ammediol, sorbyl alcohol, mannitol and inositol.In addition, C ₅-and C ₆-sugared for example glucose and fructose also are suitable for.

(oligomeric) aklylene glycol be for example (three-, four-, five-and six-) ethylene glycol, (three-, four-, five-and six) propylene glycol and (three-, four-, five-and six-) butyleneglycol.

Polyalkylene glycol is for example polytetrahydrofuran, polyoxyethylene glycol and polypropylene glycol.Preferred polyalkylene glycol is polyoxyethylene glycol and polypropylene glycol.Number-average molecular weight Mn is that the polyoxyethylene glycol of 300-5000, preferred 300-2000, preferred especially 500-1500 and polypropylene glycol and segmented copolymer thereof are preferred especially the uses.

These polyoxyethylene glycol for example obtain from BASF AG with trade(brand)name Pluriol  E, for example number-average molecular weight Mn is 300 Pluriol  E 300, number-average molecular weight Mn is 600 Piuriol  E 600, number-average molecular weight Mn is 4000 Pluriol  E 4000, and number-average molecular weight Mn is 5000 Pluriol  E 5000.The polyethylene/polypropylene glycol segmented copolymer for example obtains from BASF AG with trade(brand)name Pluronic  PE, for example number-average molecular weight Mn be 1900 and ethylene oxide content be the Pluronic  PE 3500 of 50 weight %.

If in emulsion oil-in-water, use novel cpd and/or model mixture, then can obtain stable micella.This can for example realize by action of ultrasonic waves.In addition, novel cpd and/or model mixture can use in every way, for example act as a fuel and lubricant in additive, as the corrosion inhibiting additive in liquid, aqueous, and as the inorganic and dispersion agent organic solid dispersion.In addition, novel cpd and/or model mixture can be as the tensio-active agents of washing and cleaning prescription.Contain polyoxyethylene glycol unit price group and be particularly suitable for stable inorganic and organic solid dispersion as formula (Ib) high-molecular weight compounds of hydrophilic block.

Novel cpd and/or model mixture also are suitable as the emulsifying agent of water-in-oil emulsion, wherein by plant, animal or synthetic oil or lipogenesis oil phase.These emulsion applications are at makeup or pharmaceutical field.These oil or fatty example are the Witepsol W-S 55 and the diol ester of lauric acid, tetradecanoic acid, stearic acid, palmitinic acid, oleic acid, linoleic acid plus linolenic acid.

Novel cpd and/or model mixture particularly advantageously are made of in the water-in-oil emulsion of oil phase fuel or lightweight or heavy fuel oil (HFO) therein and are used as emulsifying agent.All conventional fuel can use, for example diesel-fuel, Fuel Petroleum and kerosene.Diesel-fuel is preferred the use.

In general, the purification of novel cpd and intermediate thereof is dispensable; Only in application-specific, for example when these compounds were used as emulsifying agent in the water-in-oil emulsion of makeup or pharmaceutical field, purification can be necessary.

The present invention relates to novel cpd and/or model mixture purposes in preparation water-in-oil emulsion process, and relate to water-in-oil emulsion itself as emulsifying agent.Novel water-in-oil emulsion generally contains the oil of 95-60 weight %, the water of 3-35 weight % and at least a novel cpd and/or at least a model mixture of 0.2-10 weight %.

New-type fuel water-in type emulsion also can contain one or more C ₁-C ₄-alcohol and/or monoethylene glycol, especially monoethylene glycol.Employed C ₁-C ₄The amount of-alcohol and/or monoethylene glycol is 5-50 weight %, based on the amount meter of water.For example, by adding one or more C ₁-C ₄-alcohol and/or monoethylene glycol keep the temperature range of emulsion-stabilizing to broaden.

This New-type fuel water-in type emulsion has high stability and good efficiency in combustion processes.Can also obtain good waste gas value, the emission of cigarette ash and NOx significantly reduces, especially in diesel motor.Can realize substantially completely the burning with no residue, and in the part of combustion unit deposition not on injection nozzle, piston, ring groove, valve and the cylinder head for example.

Except mentioned component, water-in-fuel emulsion according to the present invention can have additional component.These are for example additional emulsifying agents, and as sodium lauryl sulphate, quaternary ammonium salt is ammonium nitrate for example, alkyl glycoside, Yelkin TTS, polyglycol ether and ester, single oleic acid sorbitan esters, stearate and ricinoleate, C ₁₃-oxo process alcohol ethoxylate and alkylphenol ethoxylate, and the segmented copolymer of oxyethane and propylene oxide are as the Pluronic  rank that obtains from BASF AG.Single oleic acid sorbitan esters, C ₁₃-oxo process alcohol ethoxylate and alkylphenol ethoxylate, for example octyl group-and nonyl phenol ethoxylate is preferably used as additional emulsifying agent.

One or more above-mentioned additional emulsifiers are preferred for this novel water-in-fuel emulsion with the binding substances of novel cpd and/or its mixture.

If use these additional emulsifiers, then they are to use based on the 0.5-5 weight % of total composition, the amount of preferred 1-2.5 weight %.Select the amount of additional emulsifiers, make the total amount of emulsifying agent can not surpass amount for the 0.2-10 weight % of novel cpd and/or the independent indication of its mixture.

For the preparation of novel water-in-oil emulsion, selected novel cpd and/or model mixture mix with oil, water and additional, optional available component, and emulsification in a manner known way.For example, this emulsification can be in the rotor mixing tank, utilizes mixing nozzle or carries out by means of ultrasonic probe.When the mixing nozzle of disclosed that type in the BASF AG German patent application that uses at the application number 198 56 604 on December 8th, 1998, obtain good especially result.The water-in-oil emulsion of cosmetic field can be according to preparing with the same mode of water-in-fuel emulsion.

Except surfactivity, interfacial activity and emulsifying property, this novel cpd and/or model mixture also have the oilness of improvement and suppress the corrosive effect.And they improve the wear resisting property of liquid.Therefore this novel cpd and/or model mixture are used as lubricant, fuel and liquid, aqueous additive, as radiator liquid or drilling fluid and cutting fluid.This application has constituted theme of the present invention equally.

This novel cpd and/or model mixture can directly be added in the fuel and lubricant with other component.Perhaps, this novel cpd and/or model mixture can at first mix to obtain fuel or lubricant additive concentrates with other component.These New-type fuels or lubricant additive concentrates can be added in fuel or the lubricant with undiluted form or after with one or more solvents or carrier oil dilution.The interpolation of dilute form is preferred.

Contain fuel, lubricant, fuel additive concentrate and lubricant additive concentrates and the liquid, aqueous same formation theme of the present invention and the explanation in more detail below of novel cpd and/or model mixture.

Except common component, this New-type fuel generally also contains at least a novel cpd and/or model mixture, and its content is based on the 10-5000ppm of total amount meter, preferred 20-2000ppm.

Novel lubricant contains liquid state, semi-solid state or the solid lubricant of 90-99.9 weight %, preferred 95-99.5 weight % and at least a novel cpd and/or the model mixture of 0.1-10 weight %, preferred 0.5-5 weight % usually, based on total amount.

Except common component, New-type fuel multifunctional additive for lubricating oils and lubricant additive concentrates also contain at least a novel cpd and/or model mixture, its content is 0.1-80 weight %, 0.5-60 weight % especially, based on the enriched material gross weight.

The common ingredients that is used for fuel or fuel additive concentrate is the additive that for example has detergent action, as in the applicant's of the application number 100 36 956.1 on July 28th, 2000 German patent application (14 pages are risen), in the applicant's of the application number 100 03 105.6 on January 25th, 2000 German patent application and described in the applicant's of application number PCT/EP/01/00496 the PCT patent application.Wherein said additive and the additional fuel additive of wherein describing with polar group have constituted the application's a part equally, therefore introduce for reference here.

This New-type fuel and fuel additive concentrate also can contain fuel dope, as at for example European patent application EP-A 0 277 345,0 356 725,0 476 485,0 484 736,0 539 821,0 543225,0 548 617,0 561 214,0 567 810 and 0 568 873, German patent application DE-A 3,942 860, and 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 described in.

Additional common ingredients is for example additional corrosion inhibitor, antioxidant, and stablizer, static inhibitor, organometallic compound, anti-wear agent, marker and cetane number improver, FLOW IMPROVERS, biocides is as glutaraldehyde or oxalic dialdehyde.The consumption of this biocides is normally in the 0.01-3 weight % based on the enriched material gross weight.

The example of additional corrosion inhibitor is that this salt tends to form film based on those of the ammonium salt of organic carboxyl acid class, or those of the heterocyclic aromatic hydrocarbon of using based on the corrosion protection of non-ferrous metal.

The example of stablizer is based on amine, as Ursol D, dicyclohexylamine or their derivative, or based on phenols, as 2,4-DI-tert-butylphenol compounds or 3, those of 5-di-t-butyl-4-hydroxyphenylpropionic acid.

The example of organometallic compound is ferrocene or methyl cyclopentadienyl-manganese three carboxides.

The example of cetane number improver is an organic C ₂-C ₁₀-nitric ether is as nitric acid 2-(ethyl hexyl) ester be used for the inorganic cetane number improver of water, as ammonium nitrate.Nitric acid 2-(ethyl hexyl) ester and ammonium nitrate are preferred the uses.The consumption of this cetane number improver is normally based on the 0.05-5 weight % of enriched material gross weight meter.

The suitable solvent that is used for New-type fuel and lubricant additive concentrates is aliphatic series and aromatic hydrocarbon, as solvent naphtha, Permethyl 99A., Mihagol (a kind of C ₁₀-C ₁₂The cuts of alkane), fuel and lubricant itself and carrier oil.

The carrier oil that is used to dilute fuel additive concentrate and lubricant additive concentrates equally is a mineral carrier oil (base oil) for example, especially those of viscosity grade Solvent Neutral (SN) 100-500, with based on the synthetic vectors oil of polyolefine, (gathering) ester, (alkylphenol-initiation) polyethers or (aliphatic series) (alkylphenol-initiation) polyetheramine with based on the carrier oil of alkoxylate long-chain alcohol or phenols.The example of specially suitable synthetic vectors oil is based on those of polyolefine, preferably based on polyisobutene with based on those of poly-alpha olefins, has the number-average molecular weight Mn of 400-1800.Polyoxyethylene, polyoxytrimethylene, polyoxybutylene and their mixture also are suitable carriers oil.Other suitable carriers oil and carrier oil mixture for example are described among DE-A 38 38 918, DE-A 38 26608, DE-A 41 42 241, DE-A 43 09 074, US 4,877,416 and the EP-A 0 452 328.

New aqueous liquid contains this novel cpd and/or model mixture, combines with additional general corrosion inhibitor when needed, normally based on about 1-10 weight % of total amount meter.

The following examples are used to illustrate the present invention.

Embodiment

Embodiment 1: general formula (Ia) and (Ib) preparation of compound

The composition of prepared compound is shown in Table 1.

Employed polyisobutene is the Glissopal  that obtains from BASF AG, and its number-average molecular weight Mn is 380-8400, and vinylidene endgroup content＞70 mole %, polymolecularity Mw/Mn are 1.15-1.8, and the polymer backbone structure contains 85% iso-butylene unit.This polyisobutene is as the raw material that synthesizes the succinyl oxide (PIBSA=polyisobutylene succinic anhydride) that is replaced by polyisobutenyl.

Used polyoxyethylene glycol is the Pluriol  E that obtains from BASF AG, and its number-average molecular weight Mn is 3000-5000.Used polyethylene/polypropylene glycol multipolymer is the Pluronic  PE 3500 that obtains from BASF AG, and its number-average molecular weight Mn is 1900, and ethylene oxide content is 50 weight %.

Used solvent is heptane, Mihagol (a kind of C ₁₀-C ₁₂The cuts of alkane is from Wintershall) and Solvesso  150 (a kind of aromatic hydrocarbons mixture is from ExxonMobilChemical).

Used ion-exchanger is the ion-exchanger that obtains with trade(brand)name Ambossol  from Clariant.

Polyisobutene is carried out the operation that maleinization obtains corresponding succinyl oxide carry out, for example be described among DE-A 195 19 042, DE-A 43 19 671 and the DE-A 43 19 672 according to the known method method.

The compound of gained is by acid number, hydroxyl value, viscosity and/or IR spectral characterization.Hydroxyl value is used high boiling solvent and is proofreaied and correct this solvent and measure, that is, the hydroxyl value of detection compound in each solvent is extrapolated to pure substance then.At low boiling point solvent for example under the situation of heptane, remove by distillation and to desolvate, and measure the hydroxyl value of pure substance.

Viscosity is measured according to DIN 51562.

Table 1: the formula (Ia) or (Ib) composition of compound

Compound	???Glissopal ?Mn??????Mw/Mn	The hydrolysis value of PIBSA	The polar reaction agent
				A	?550?????1.23	???148	?(HO-CH 2-CH 2-) 2NH
B	?550?????1.23	???148	?(HO-CH 2) 3-CNH 2
				C	?750?????1.31	???120	The D-sorbyl alcohol
D	?380?????1.15	???210	?PluriolE300
				E	?550?????1.23	???147	Pluriol  E300 and (HO-CH 2-CH 2-) 2NH
F	?1000????1.31	???95	?PluriolE600
				G	?2300????1.52	???40	?PluriolE1500
H	?5200????1.38	???18.3	?PluriolE4000
				I	?8400????1.45	???12.0	?PluriolE5000
J	?1000????1.31	???95	?(HO-CH 2-CH 2-) 2NH
				K	?1000????1.31	???95	?PluronicE3500
L	?550?????1.31	???148	Choline
				M	?1000????1.31 ?2300????1.52	???95 ???40	Monoethylene glycol

The preparation of compd A:

In the 1L four neck flasks of being furnished with agitator, dropping funnel and thermopair, add the PIBSA550 of 250g, be heated to 90 ℃.In 5 minutes, be metered into the 67g diethanolamine via dropping funnel.This mixture is heated to 130 ℃ or 170 ℃ gradually.After 2 hours, filter brown reaction product 170 ℃ of maintenances in 100 ℃.

The preparation of compd B:

The Solvesso  150 of PIBSA550, the 650g of adding 525g and the Tutofusin tris (TRIS) of 175g in the 2L four neck flasks of being furnished with agitator, distillation bridge and thermopair.This mixture is heated to 130 ℃ or 170 ℃ gradually.The water that discharges is removed by nitrogen gas stream; Reaction times is 3 hours.Proofread and correct this solvent, recording hydroxyl value is 250.

The preparation of Compound C:

In the 1L four neck flasks of being furnished with agitator, distillation bridge and thermopair, add the PIBSA750 of 310g and the D-sorbyl alcohol of 60g.This mixture is heated to 160 ℃ or 220 ℃ gradually.The water that discharges is removed by nitrogen gas stream; 220 ℃ keep 3 hours after, dilute filtered while hot with the Mihagol of 200g.Obtain xanchromatic sticky product solution (65%).

The preparation of Compound D:

The Pluriol  E300 that adds 350g in the 2L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 380 in the 350g heptane of 650g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.Decompression (350 millibars) distills out heptane in this process.After 3 hours, obtain yellow product 140 ℃ of maintenances, viscosity is 105mm ²/ s (100 ℃); Hydroxyl value is 70; Acid number is 73; IR: at 1735cm ^-1Strong bands of a spectrum (ester) are arranged.

The preparation of compd E:

The Pluriol  E300 that adds 300g in the 2L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 550 in the 450g heptane of 750g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.Decompression (350 millibars) distills out heptane in this process.After 3 hours, be added dropwise to the 105g diethanolamine 140 ℃ of maintenances in 95 ℃.95 ℃ keep 20 minutes again after, filtered while hot yellowish brown product.Hydroxyl value is 55; IR: at 1736cm ^-1Strong bands of a spectrum (ester) are arranged.

The preparation of compound F 17-hydroxy-corticosterone:

The Pluriol  E600 that adds 400g in the 2L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 1000 in the 450g heptane of 790g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.Decompression (350 millibars) distills out heptane in this process.After 3 hours, obtaining viscosity is 1650mm 140 ℃ of maintenances ²The yellow product of/s (100 ℃).Hydroxyl value is 43; Acid number is 40; IR: at 1734cm ^-1Strong bands of a spectrum (ester) are arranged.

The preparation of compound G:

The Plurioi  E1500 that adds 150g in the 1L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 2300 in 300gMihagol of 280g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.After 3 hours, obtain the highly viscous solution of xanchromatic 140 ℃ of maintenances.Its viscosity is 1750mm ²/ s, 100 ℃; Hydroxyl value is 9; Acid number is 8.1; IR: at 1736cm ^-1Bands of a spectrum are arranged.

The preparation of compound H:

The Pluriol  E4000 that adds 150g in the 1L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 5200 in 300gMihagol of 250g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.After 3 hours, obtain cream-coloured wax 140 ℃ of maintenances.Its hydroxyl value is 4.3; Acid number is 3.5; IR: at 1736cm ^-1Bands of a spectrum (ester) are arranged.

The preparation of Compound I:

According to the similar mode of compound H, (basic: reactive PIB 8400 from PIBSA; Mw/Mn=1.45) and Pluriol  E5000 synthesize.Separating the product that obtains is milky wax (60% concentration in Mihagol); IR: at 1737cm ^-1

The preparation of comparative example 1 compound J

According to the similar mode of compd A, (basic: reactive PIB 1000 from PIBSA 1000; Mw/Mn=1.31) and diethanolamine synthesize (also referring to US4708753).Separating the product that obtains is brown highly viscous liquid, and its wetting ability A-R content is lower than compd A.

The preparation of compound K:

According to the similar mode of compound F 17-hydroxy-corticosterone, (basic: reactive PIB 1000 from PIBSA 1000; Mw/Mn=1.31) and Pluriol  PE3500 synthesize.Separating the product that obtains is tenne highly viscous liquid.Its viscosity is 2100mm ²/ s; 100 ℃.

The preparation of compound L:

The choline methanol solution (from Fluka) of 45% concentration of adding 75g and the Mihagol of 150g in the 1L four neck flasks of being furnished with agitator, dropping funnel and thermopair.Remove methyl alcohol in 50 ℃ of decompressions (50 millibars) (45 minutes) then.The PIBSA 550 of 200g is metered in this suspension, and in 15 minutes with this mixture heating up to 90 ℃.After 60 minutes, temperature is elevated to 170 ℃, restir 2 hours.Filter brown reaction product in 100 ℃.

Be used for the preparation of comparative example 2 compound M:

The PIBSA 1000 of PIBSA2300, the 200g of adding 300g and the Mihagol of 200g are heated to 95 ℃ in the 1L four neck flasks of being furnished with agitator, dropping funnel and thermopair.Be metered into 17.2g ethylene glycol in 95 ℃.With this mixture heating up to 130 ℃, and under this temperature restir 3 hours.Filter brown reaction product in 100 ℃.

According to the 34th page Embodiment C-1 preparation comparative example's 2 emulsifying agent among the WO00/15740.

Be used for the preparation of comparative example 3 compound N:

(according to carrying out with the similar mode of compound F 17-hydroxy-corticosterone.But the A-R content of compound F 17-hydroxy-corticosterone is 35.3%, and the content of the hydrophilic segment A-R in the compound N is 15.4%)

The Pluriol  E200 that adds 100g in the 2L four neck flasks of being furnished with agitator, dropping funnel and thermopair is in 30 minutes, under reduced pressure in 90 ℃ of degassings.In 5 minutes, the solution of PIBSA 1000 in the 450g heptane of 590g is metered in 80 ℃ via dropping funnel.This mixture is heated to 110 ℃ or 140 ℃ gradually.Decompression (350 millibars) distills out heptane in this process.After 3 hours, obtaining viscosity is 1450mm 140 ℃ of maintenances ²The amber product of/s (100 ℃).

Embodiment 2: the preparation of water-in-fuel emulsion

The preparation or the composition of fuel mixture are listed in the table 2.

Wetting ability or water soluble ingredient are dissolved in aqueous phase in advance, and lipophilic ingredients is dissolved in the diesel oil.In 15 minutes, use Ultra-Turrax  (Jahnke and Kunkel laboratory equipment T25) with the speed of 2400rpm with this mixture of 500g and 100ml water homogenizing.The described similar mode of DE-A198 56 604 (on December 8th, 1998 submitted) according to the applicant is carried out the industrial-scale production and the engine test of emulsion, uses mixing nozzle here.Pressure in mixing equipment is 50-200 crust, preferred 120 crust (before orifice plate), and total conversion rate is 12kg/h.

Table 2: the composition of emulsion

^*Used microbicide is or oxalic dialdehyde or glutaraldehyde.

In embodiment 1,2,6 and 7, use the compound of novel low molecular weight amount, in embodiment 3,4 and 5, use the model mixture of lower molecular weight and high-molecular weight compounds.

Embodiment compound (weight %)	????1	????2	????3	????4	????5	????6	????7	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3
											??A	????1.4	????-	????-	????-	????1.5	????-	????-	????-	????-	????-
??B	????-	????-	????-	????-	????-	????-	????-	????-	????-	????-
											??C 13The oxo process alcohol ethoxylate has 5 [CH 2-CH 2-O-] unit	????0.2	????0.2	????-	????-	????-	????0.2	????0.3	????0.3	????0.3	????0.3
Alkylphenol ethoxylate	????0.2	????-	????0.2	????0.3	????0.3	????-	????-	????-	????-	????-
											??C	????-	????-	????-	????1.3	????-	????-	????-	????-	????-	????-
??D	????-	????-	????1.5	????-	????-	????-	????0.5	????-	????-	????-
											??E	????-	????-	????-	????-	????-	????1.8	????-	????-	????-	????-
??F	????-	????0.3	????-	????-	????-	????-	????-	????-	????-	????-
											??G	????-	????-	????0.2	????-	????0.3	????-	????-	????-	????-	????-
??H	????-	????-	????-	????-	????-	????-	????-	????-	????-	????-
											??I	????-	????-	????-	????0.4	????-	????-	????-	????-	????-	????-
??J	????-	????-	????-	????-	????-	????-	????-	????1.8	????-	????-
											??K	????-	????-	????-	????-	????-	????-	????1.0	????-	????-	????-
??L	????-	????1.6	????-	????-	????-	????-	????-	????-	????-	????-
											??M	????-	????-	????-	????-	????-	????-	????-	????-	????1.7	????-
??N	????-	????-	????-	????-	????-	????-	????-	????-	????-	????1.7
											Diesel oil (EN 590)	????76.3	????76.0	????76.1	????76.2	????76.0	????76.5	????76.2	????76.0	????76.1	????76.1
Water	????20	????20	????20	????15	????20	????15	????20	????15	????15	????15
											Methyl alcohol	????-	????-	????-	????2	????-	????3	????-	????-	????-	????-
Ethylene glycol	????-	????-	????-	????3	????-	????2	????-	????5	????5	????5
											Microbicide *	????0.4	????0.4	????0.5	????0.3	????0.4	????-	????0.5	????0.4	????0.4	????0.4
??NH 4NO 3	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5

Embodiment 3: the stability of research water-in-fuel emulsion

The size of water droplet detects with physics mode by laser diffraction (X3,2 values) with Malvern Mastersizer 2000 (from Malvern InstrumentsGmbH.).For example at Terence Allen, Particle Size Measurement, the 1st volume has been described detection method in the 5th edition (Kluwer Academic Publishers, Dordrecht, Netherlands, 1999).According in esse size-grade distribution, except laser diffractometry, other method for example dynamic light scattering, single-particle counting and ultrasonic-attenuation method also is suitable.

The size of water droplet is measuring of quality of the emulsion.Water droplet size is more little, and emulsion is just good more or stable more.The analog value of water droplet size (X3,2 values) is listed in the table 3.Table 3 has shown that a part of emulsion has comparison than the remarkable littler drop size of emulsion when using novel cpd and model mixture.From the stability data that stores measuring as seen, drop size is a kind of means of weighing the room temperature stability of emulsion really.Emulsion with big drop size also has the relatively poor shelf lives.

Table 3: the drop size of water-in-fuel emulsion and stability

Embodiment	??1	??2	??3	??4	??5	??6	??7	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3
											Drop size (X3,2 values) [μ m]	??2.9	??2.2	??1.0	??3.1	??2.5	??3.2	??2.7	????5.4	??6.2	??6.8
Store experiment (room temperature) *[% emulsion]	??86	??＞95	??＞95	??91	??89	??79	??77	????61	??58	??49
											Store experiment (70 ℃) **[% emulsion]	??91	??100	??100	??89	??93	??80	??82	????73	??75	??69
Store experiment (20 ℃) **[% emulsion]	??-	??65	??-	??91	??95	??89	??-	????62	??64	??63

^{* 1}2 weeks; ^*1 week

In 20 ℃ (12 weeks) with in addition in the stability that in static state storage experiment, detects emulsion under the situation of change temperature (20 ℃ and 70 ℃, each 1 week).For this reason, adding this emulsion in 100 milliliters of graduated cylinders step by step, its quality is visual assessment under the described conditions.

Compare with the emulsifying agent (comparative example) that uses prior art, it is significant observing the improvement of shelf lives in some cases under the situation of using New-type emulsifier and its mixture.Carry out-20 ℃ storage experimental evaluation then in room temperature.Emulsion according to embodiment 2 is more even after heating, also is like this during even without adding frostproofer (for example monoethylene glycol).Otherwise, after heating or even i.e. breakdown of emulsion during heating occurs being separated.

New Emulsion with according to WO00/15740 (Embodiment C-1,34 pages, Comparative Examples 2) emulsion is compared, and proves that the combination of lower-molecular-weight component and high molecular weight component obtains corresponding bridge joint compound, and this causes than the remarkable worse emulsifying agent of the model mixture of isolated compound.

Embodiment 4: new (I) compound is as antirust and purposes anti-wear additive

The iron plate of 20 * 40mm in the emulsion that immersion (similar to ASTM D-665) prepares, stores 24 hours in 40 ± 1 ℃ then with 40 μ m granulated glass sphere sandblasts in embodiment 2.After 24 hours, observe the situation that iron plate gets rusty.Here:

++ expression is not got rusty;

+ 0 expression has rusty stain slightly;

-0 expression is got rusty above 25% of test piece area;

--expression is got rusty above 50% of test piece area;

As shown in table 4, in some cases, when using novel cpd, rusty stain is only arranged slightly as corrosion inhibiting additive.By contrast, when using C ₁₃During the oxo process alcohol ethoxylate, occurring getting rusty above on 50% the test piece area.

Embodiment 5: purposes and the wear resisting property thereof of new (I) compound in fuel

In each case, the compound dissolution shown in the table in diesel oil, do not add additive (Miro, Karlsruhe).The concentration of additive in diesel oil is 75ppm.Wear resisting property is measured by HFRR experiment (experiment of high-frequency roller bar), carries out according to ISO 12156-1.Detect the length of gained groove, be used to weigh abrasive conditions.Groove is short more, and the wear protection performance of the additive that is added is good more.The diesel oil that does not contain additive is used for comparison.As shown in table 4, novel cpd has anti-wear effect.

Table 4:

Additive	Trench length [μ m]	Corrosion
			Compd B	????380	????+0
Compound C	????490	????-0
			Compound D	????315	????+0
Compd E	????295	????++
			Compound F 17-hydroxy-corticosterone	????320	????++
Compound G	????420	????+0
			Compound J	????495	????-0
Additive-free	????605	????--

Claims (16)

1. A compound of general formula (Ia) or (Ib),

Wherein L ^a is the polyisobutenyl group whose number average molecular weight Mn is 300-1000, L ^b is a polyisobutylene group with a number average molecular weight Mn of 2000-20000, -A- is -O-, -N(H)- or -N(R ¹ )-, M ⁺ is H ⁺ , alkali metal ion, 0.5 alkaline earth metal ion or NH ₄ ⁺ , wherein one or more H in NH ₄ ⁺ can be replaced by an alkyl group, R is a linear or branched saturated hydrocarbon group with at least one substituent selected from OH, NH ₂ and NH ₃ ⁺ , and contains one or more C(O) groups when required, and Contains one or more non-adjacent -O-, and/or secondary and/or tertiary amines, wherein one or more H in the _NH2- or _NH3 ⁺ group may be substituted by an alkyl group, and R ¹ is a straight-chain or branched saturated hydrocarbon group, which carries one or more substituents selected from OH, NH ₂ , NH ₃ ⁺ and C(O)H when necessary, and contains one or a plurality of non-adjacent -O-, and/or secondary and/or tertiary amines, wherein one or more H in the _NH2- or _NH3 ⁺ group may be substituted by an alkyl group, and In the compound of general formula (Ia) or (Ib), the proportion of A-R is at least 20% by weight. 2. The compound according to claim 1, wherein La is a polyisobutenyl group with a number average molecular weight Mn of 350-950, especially 350-650, and L ^b is a number average ^molecular weight Mn of 2000-12000, especially 2300-5000 of polyisobutylene. 3. The compound according to claim 1 or 2, wherein L ^a and L ^b are each polyisobutenyl having a polydispersity ≦3.0, preferably 1.1-2.5, particularly preferably 1.1-2.0. 4. Compounds according to any one of claims 1 to 3, wherein L ^a and L ^b are each polyisobutenyl consisting of at least 80% by weight of isobutenyl units. 5. The compound according to any one of claims 1-4, wherein in the compound of general formula (Ia) or (Ib) the proportion of A-R is at least 25% by weight, in particular 35-60% by weight. 6. The compound according to any one of claims 1-5, wherein A is -O-, and R is a monovalent group of an oligomer or polymer of ethylene oxide and/or propylene oxide, or R is Monovalent group for block copolymers of ethylene oxide and propylene oxide. 7. A mixture comprising: (a) not more than 99% by weight, preferably 98-80% by weight, particularly preferably 97-85% by weight, of at least one compound of formula (Ia),

(b) at least 1% by weight, preferably 2-20% by weight, particularly preferably 3-15% by weight, of at least one compound of the formula (Ib), Wherein L ^a is a polyisobutenyl group whose number average molecular weight Mn is 300-1000, and L ^b is a polyisobutenyl group whose number average molecular weight Mn is 2000-20000, -A- is -O-, -N(H)- or -N(R ¹ )-, M ⁺ is H ⁺ , alkali metal ion, 0.5 alkaline earth metal ion or NH ₄ ⁺ , wherein one or more H in NH ₄ ⁺ can be replaced by an alkyl group, R is a linear or branched saturated hydrocarbon group with at least one substituent selected from OH, NH ₂ and NH ₃ ⁺ , and contains one or more C(O)H groups when required, and containing one or more non-adjacent -O-, and/or secondary and/or tertiary amines, wherein one or more H in the _NH2- or _NH3 ⁺ group may be substituted by an alkyl group, and R ¹ is a straight-chain or branched saturated hydrocarbon group, which carries one or more substituents selected from OH, NH ₂ , NH ₃ ⁺ and C(O)H when necessary, and contains one or a plurality of non-adjacent -O-, and/or secondary and/or tertiary amines, wherein one or more H in the _NH2- or _NH3 ⁺ group may be substituted by an alkyl group, and In compounds of general formula (Ia) the proportion of A-R is at least 10% by weight, and in compounds of general formula (Ib) the proportion of A-R is at least 20% by weight. 8. The mixture according to claim 7, wherein in the compound of formula (Ia) the proportion of A-R is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably 35-60% by weight, and /or in the compound of formula (Ib), the proportion of A-R is at least 25% by weight, especially 35-60% by weight. 9. The mixture according to claim 7 or 8, wherein L ^a and L ^b are each polyisobutenyl consisting of at least 80% by weight of isobutenyl units. 10. A method for preparing any one of claims 1-6 of formula (Ia) and (Ib) compound, wherein polyisobutylene is mixed with fumaryl chloride, fumaric acid, maleic acid chloride, maleic acid or maleic acid Anhydride reaction, the resulting reaction product with ethylene oxide, propylene oxide, alkanolamine, polyamine, oligomeric alcohol, polyol, oligoalkylene glycol, polyalkylene glycol, carbohydrate or The sugars are reacted and, if desired, the free hydroxyl groups present are converted to the corresponding salts by _NH3 , amines or alkali or alkaline earth metal salts. 11. according to the compound of formula (Ia) and/or (Ib) according to any one of claims 1-6 and/or according to the mixture of any one of claims 7-9 in fuels, lubricants or fuel additives and lubricants Use in additive concentrates as surface-active substances, as emulsifiers, as anti-wear additives, as lubricity additives or as corrosion-inhibiting additives, or as corrosion-inhibiting additives in aqueous liquids. 12. Use according to claim 11, wherein the compounds and/or mixtures are used as emulsifiers in the preparation of water-in-oil emulsions, in particular water-in-fuel emulsions, or as an additive in industrial and cosmetic washing and cleaning ingredients. Surfactant. 13. A fuel, lubricant, fuel additive concentrate, lubricant additive concentrate or aqueous liquid containing a compound of formula (Ia) and/or (Ib) according to any one of claims 1-6 and/or according to A mixture according to any one of claims 7-9, preferably a water-in-fuel emulsion, containing 60-95% by weight of fuel, preferably diesel, 3-35% by weight of water and as emulsifier 0.2-10% by weight, preferably 0.5-5% by weight of one or more compounds of formula (Ia) and/or (Ib) according to any one of claims 1-6 and/or mixtures according to any one of claims 7-9. 14. A washing or cleaning ingredient comprising a compound of formula (Ia) and/or (Ib) according to any one of claims 1-6 and/or a mixture according to any one of claims 7-9. 15. Emulsion according to claim 13, wherein in addition to one or more compounds of formula (Ia) and/or (Ib) one or more further emulsifiers are present, 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. 16. A process for producing an emulsion according to claim 13 or 15, wherein the components are mixed with one another and emulsified in a manner known per se, preferably in a mixing nozzle.