Branched primary alkyl amines as additives for gasoline fuels

Abstract

Certain branched amines are useful as additives for gasoline fuels, especially for reducing injector nozzle fouling in direct injection spark ignition engines.

1 - 16 . (canceled) 
     
     
         17 : A method for reducing injector nozzle fouling in a direct injection spark ignition engine, the method comprising:
 adding a fuel additive to an unleaded gasoline composition comprising a major proportion of a gasoline suitable for the spark ignition engine, wherein the fuel additive is a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by  1 H-NMR spectroscopy.   
     
     
         18 : A method for improving storage stability and/or formulability of a fuel additive package for gasoline, the method comprising:
 adding an additive to the fuel additive package, wherein the additive is a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by  1 H-NMR spectroscopy.   
     
     
         19 : The method according to  claim 17 , wherein the gasoline composition further comprises at least one deposit control agent selected from the group consisting of
 quaternary ammonium compounds,   Mannich adducts, and   polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range of 300 to 5000.   
     
     
         20 : The method according to  claim 17 , wherein the branched primary alkyl amine is selected from the group consisting of
 2-propyl heptyl amine,   branched nonyl amine,   branched tridecyl amine, and   branched heptadecyl amine.   
     
     
         21 : An unleaded gasoline composition, comprising:
 a major proportion of a gasoline suitable for a spark ignition engine, and   10 to 3000 ppmw, based on the unleaded gasoline composition, of a branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by  1 H-NMR spectroscopy.   
     
     
         22 : The unleaded gasoline composition according to  claim 21 , further comprising:
 at least one deposit control agent selected from the group consisting of   from 10 to 100 ppm by weight of a quaternary ammonium compound,   from 10 to 1000 ppm by weight of a Mannich adduct, and   from 10 to 1000 ppm by weight of a polyalkenemono- or polyalkenepolyamine having a number average molecular weight in the range of 300 to 5000.   
     
     
         23 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of the formula
     + NR 1 R 2 R 3 R 4 A −     in which   A −  stands for an anion, a carboxylate R 5 COO − , or a carbonate R 5 O—COO − , and   R 1 , R 2 , R 3 , R 4 , and R 5  independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, and   R 5  additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 20 carbon atoms.   
     
     
         24 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group, onto a polycarboxylic anhydride compound, and subsequent quaternization in the presence of an acid or in an acid-free manner. 
     
     
         25 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         PIB stands for a polyisobutenyl residue having a number average molecular weight M n  of from 550 to 2300 g/mol, 
         R stands for a C 1 - to C 4 -alkyl or hydroxy-C 1 - to C 4 -alkyl, and 
         A −  stands for an anion. 
       
     
     
         26 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         PIB stands for a polyisobutenyl residue having a number average molecular weight M n  of from 550 to 2300 g/mol, and 
         R stands for a hydroxy-C 1 - to C 4 -alkyl. 
       
     
     
         27 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         PIB stands for a polyisobutenyl residue having a number average molecular weight M n  of from 550 to 2300 g/mol, 
         R stands for an C 1 - to C 4 -alkyl or hydroxy-C 1 - to C 4 -alkyl, and 
         A −  stands for an anion. 
       
     
     
         28 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         R a  stands for C 1 -C 20 -alkyl, 
         R b  stands for a hydroxy-C 1 - to C 4 -alkyl, and 
         A −  stands for an anion. 
       
     
     
         29 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         X i  for i=1 to n and 1 to m, are independently of another selected from the group consisting of —CH 2 —CH 2 —O—, —CH 2 —CH(CH 3 )—O—, —CH(CH 3 )—CH 2 —O—, —CH 2 —C(CH 3 ) 2 —O—, —C(CH 3 ) 2 —CH 2 —O—, —CH 2 —CH(C 2 H 5 )—O—, —CH(C 2 H 5 )—CH 2 —O—, and —CH(CH 3 )—CH(CH 3 )—O—, 
         m and n independently of another are positive integers, with the proviso that the sum (m+n) is from 2 to 50, 
         R stands for an C 1 - to C 4 -alkyl, and 
         A −  stands for an anion. 
       
     
     
         30 : The unleaded gasoline composition according to  claim 22 , wherein the at least one deposit control agent is of formula 
       
         
           
           
               
               
           
         
         wherein in this formula 
         R a  and R b  independently of another stand for C 1 -C 20 -alkyl or hydroxy-C 1 - to C 4 -alkyl, and 
         A −  stands for an anion. 
       
     
     
         31 : A fuel additive package for gasoline fuels, comprising:
 at least one branched primary alkyl amine, with an alkyl group having from 8 to 22 carbon atoms and with a branching of at least 1.0 determined by  1 H-NMR spectroscopy,   at least one deposit control agent selected from the group consisting of
 quaternary ammonium compounds, 
 Mannich adducts, and 
 polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and 
   optionally, at least one further gasoline fuel additive selected from the group consisting of
 corrosion inhibitors, 
 carrier oils, and 
 solvents. 
   
     
     
         32 : The unleaded gasoline composition according to  claim 21 , wherein the alkyl group has 13 carbon atoms. 
     
     
         33 : The unleaded gasoline composition according to  claim 21 , wherein the branching is from at least 1.5 to 7.0 as determined by  1 H-NMR spectroscopy. 
     
     
         34 : The unleaded gasoline composition according to  claim 23 , wherein
 R 1 , R 2 , R 3 , R 4 , and R 5  independently of another are unsubstituted, linear or branched alkyl, alkenyl or hydroalkyl residues with 1 to 100 carbon atoms.   
     
     
         35 : The unleaded gasoline composition according to  claim 24 , wherein the quaternization is with an epoxide in the absence of free acid, or with a carboxylic ester. 
     
     
         36 : The unleaded gasoline composition according to  claim 35 , wherein the epoxide is styrene or propylene oxide, or wherein the carboxylic ester is dimethyl oxalate or methyl salicylate.