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

Abstract

Low molecular weight and high molecular weight two-block emulsifiers, in particular based on polyisobutylene, of the formula (Ia) or (Ib) and mixtures thereof where L a is a polyisobutylenyl group having a number average molecular weight M n of from 300 to 1 000 and L b is a polyisobutylenyl group having a number average molecular weight M n of from 2 000 to 20 000, -A- is —O—, —N(H) or —N(R 1 )—, M + is H + or an alkali metal ion, 0.5 alkaline earth metal ion or NH 4 + , where one or more H in NH 4 + may be replaced by alkyl, R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH 2 and NH 3 + and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring —O— and/or secondary amines and/or tertiary amines, where one or more H in the NH 2 — or NH 3 + groups may be replaced by alkyl, and R 1 is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH 2 , NH 3 + and C(O)H and, if required, contains one or more nonneighboring —O— and/or secondary amines and/or tertiary amines, and where one or more H in the NH 2 — or NH 3 + groups may be replaced by alkyl, and the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 20% by weight, are described.

We claim:  
     
         1 . A compound of the formula (Ia) or (Ib)  
       
         
           
           
               
               
           
         
         where L a  is a polyisobutylenyl group having a number average molecular weight M n  of from 300 to 1 000,  
         L is a polyisobutylenyl group having a number average molecular weight M n  of from 2 000 to 20 000,  
         -A- is —O—, —N(H)— or —N(R 1 )—,  
         M +  is H +  or an alkali metal ion, 0.5 alkaline earth metal ion or NH 4   + , where one or more H in NH 4   +  may be replaced by alkyl,  
         R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH 2  and NH 3   +  and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring —O— and/or secondary amines and/or tertiary amines, where one or more H in the NH 2 — or NH 3   +  groups may be replaced by alkyl, and  
         R 1  is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH 2 , NH 3   +  and C(O)H and, if required, contains one or more nonneighboring —O— and/or secondary amines and/or tertiary amines, and where one or more H in the NH 2 — or NH 3   +  groups may be replaced by alkyl, and  
         the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 20% by weight.  
       
     
     
         2 . The compound as claimed in  claim 1 , wherein L a  is a polyisobutylenyl group having a number average molecular weight M n  of from 350 to 950, in particular from 350 to 650, and L b  is a polyisobutylenyl group having a number average molecular weight of from 2 000 to 12 000, in particular from 2 300 to 5 000.  
     
     
         3 . The compound as claimed in  claim 1  or  2 , wherein L a  and L b  are each a polyisobutylenyl group which has a polydispersity of ≦3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0.  
     
     
         4 . The compound as claimed in any of  claims 1  to  3 , wherein L a  and L b  are each a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units.  
     
     
         5 . The compound as claimed in any of  claims 1  to  4 , wherein the proportion of A-R in the compound of the formula (Ia) or (Ib) is at least 25, in particular from 35 to 60, % by weight.  
     
     
         6 . The compound as claimed in any of  claims 1  to  5 , wherein A is —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 oxide and propylene oxide.  
     
     
         7 . A mixture containing 
 (a) not more than 99, preferably from 98 to 80, particularly preferably from 97 to 85, % by weight of at least one compound of the formula (Ia),                          (b) at least 1, preferably from 2 to 20, particularly preferably from 3 to 15, % by weight of at least one compound of the formula (Ib),    where L a  is a polyisobutylenyl group having a number average molecular weight M n  of from 300 to 1 000 and L b  is a polyisobutylenyl group having a number average molecular weight M n  of from 2 000 to 20 00,    -A- is —O—, —N(H)— or —N(R 1 )—,    M +  is H +  or an alkali metal ion, 0.5 alkaline earth metal ion or NH 4   + , where one or more H in NH 4   +  may be replaced by alkyl,    R is a linear or branched saturated hydrocarbon radical which carries at least one substituent selected from the group consisting of OH, NH 2  and NH 3   +  and, if required, one or more C(O)H groups and, if required, contains one or more nonneighboring —O—— and/or secondary amines and/or tertiary amines, where one or more H in the NH 2 — or NH 3   +  groups may be replaced by alkyl, and    R 1  is a linear or branched saturated hydrocarbon radical which, if required, carries one or more substituents selected from the group consisting of OH, NH 2 , NH 3   +  and C(O)H and, if required, contains one or more nonneighboring —O— and/or secondary amines and/or tertiary amines, and where one or more H in the NH 2 — or NH 3   +  groups may be replaced by alkyl, and    the proportion of A-R in the compound of the formula (Ia) is at least 10% by weight and that in the compound of the formula (Ib) is at least 20% by weight.    
     
     
         8 . A mixture as claimed in  claim 7 , wherein the proportion of A-R in the compound of the formula (Ia) is at least 15, preferably at least 20, particularly preferably at least 25, very particularly preferably from 35 to 60, % by weight and/or that in the compound of the formula (Ib) is at least 25, in particular from 35 to 60, % by weight.  
     
     
         9 . The mixture as claimed in  claim 7  or 8, wherein L a  and/or L b  are each a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units.  
     
     
         10 . A process for the preparation of compounds of the formula (Ia) and (Ib) as claimed in any of  claims 1  to  6 , in which polyisobutylene is reacted with fumaryl dichloride, fumaric acid, maleyl dichloride, maleic acid or maleic anhydride, 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 is, if required, converted with NH 3 , an amine or an alkali metal salt or alkaline earth metal salt into the corresponding salt.  
     
     
         11 . The use of a compound of the formula (Ia) and/or (Ib) as claimed in any of  claims 1  to  6  and/or of a mixture as claimed in any of  claims 7  to  9  as a surface-active substance, as an emulsifier, as an antiwear additive, as a lubricity additive or as a corrosion-inhibiting additive in fuels, lubricants or fuel additive and lubricant additive concentrates or as a corrosion-inhibiting additive in water-containing liquids.  
     
     
         12 . The use as claimed in  claim 11 , the compound and/or the mixture being used as an emulsifier in the preparation of water-in-oil emulsions, in particular of water-in-fuel emulsions, or as a surfactant for industrial and cosmetic washing and cleaning formulations.  
     
     
         13 . A fuel, lubricant, fuel additive concentrate, lubricant additive concentrate or water-containing liquid containing one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of  claims 1  to  6  and/or a mixture as claimed in any of  claims 7  to  9 , preferably a water-in-fuel emulsion containing from 60 to 95% by weight of fuel, preferably diesel fuel, from 3 to 35% by weight of water and from 0.2 to 10, preferably from 0.5 to 5, % by weight of one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of claims  1  to 6 and/or of a mixture as claimed in any of  claims 7  to  9  as an emulsifier.  
     
     
         14 . A washing or cleaning formulation containing one or more compounds of the formula (Ia) and/or (Ib) as claimed in any of  claims 1  to  6  and/or a mixture as claimed in any of  claims 7  to  9 .  
     
     
         15 . The emulsion as claimed in  claim 13 , wherein, in addition to one or more compounds of the formula (Ia) and/or (Ib), one or more further emulsifiers, preferably sorbitan monooleate, C 13  oxo alcohol ethoxylates or alkylphenol ethoxylates, and/or one or more biocides, preferably NH 4 NO 3  and/or glyoxal, particularly preferably glyoxal, are present.  
     
     
         16 . A process for the preparation of an emulsion as claimed in  claim 13  or  15 , wherein the respective components are mixed with one another and are emulsified in a manner known per se, preferably in a mixing nozzle.