Gasoline additive for direct injection gasoline engine

Abstract

Gasoline additives of the present invention comprise nitrogen-containing compounds obtained by hydrolyzing a polyoxyalkylene glycol derivative resulting from polymerization of an epoxy compound using a suitable ketimine compound as a reaction initiator or by modifying the terminal ends of a polybutene compound with amine. Blending the inventive gasoline additive to a base gasoline can produce a gasoline composition which is suitable for use in direct injection gasoline engine.

What is claimed is:  
     
         1 . A gasoline additive for a direct injection gasoline engine which comprises at least one nitrogen-containing compound selected from the group consisting of a compound (1A) and a polybutenylamine compound: 
 said compound (1A) being represented by the formula  
                 
   wherein R 1  is selected from the group consisting of a hydrogen and a C 1 -C 30  hydrocarbon group, R 2 , R 3 , R 4  and R 5  are each independently selected from the group consisting of a hydrogen a C 1 -C 16  hydrocarbon group and a group of formula (2a) below, a is an integer from 1 to 200, R 6  is a C 1 -C 10  hydrocarbon group, b is either 0 or 1, Z is a group selected from Group A below, c is either 0 or 1, X is a group selected from Group B below, d is an integer from 1 to 3, e is an integer from 0 to 2 and the sum of d and e is equal to 3,    said formula (2a) being  
                 
   wherein R 7  and R 8  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  hydrocarbon group and a C 2 -C 10  alkoxyalkyl group, R 9  is either a C 2 -C 6  alkylene group or a C 4 -C 10  alkylene group having an alkoxyalkyl substituent, R 10  is hydrogen or a C 1 -C 30  hydrocarbon group, and f is an integer from 0 to 50;    said Group A being constituted by 
 (A1) —O—CO— 
 (A2) —CO — 
 (A3) —O—CO—R 11 —
 wherein R 11  is a C 1 -C 8  alkylene group,  
 
 (A4) —O—CO—O—R 12 —
 wherein R 12  is a C 1 -C 6  alkylene group, and  
 
 (A5) —CO—O—R 13 —
 wherein R 13  is a C 1 -C 6  alkylene group,  
 
 said Group B being constituted by 
 (B1) hydrogen,  
 (B2) a C 1 -C 30  hydrocarbon group,  
 (B3) an alkanol group represented by the formula 
 —R 14 —OH  (3a) wherein R 14  is a C 1 -C 6  alkylene group,    
 (B4) a nitrogen-containing group represented by the formula  
                 

 wherein R 15  is a C 2 -C 6  alkylene group, R 16  is selected form the group consisting of a hydrogen, a C 1 -C 4  alkyl group or a group of formula (3a), R 17  is selected from the group consisting of a hydrogen, a C 1 -C 30  hydrocarbon group and a group of formula (3a), and g is an integer from 1 to 5, and  
 
 (B5) a group represented by the formula  
                 

 wherein R 18  is a C 2 -C 6  alkylene group, R 19 , R 20 , R 21  and R 22  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  hydrocarbon group and a hydroxyl group, Y is selected from the group consisting of a methylene group, a methylene group substituted by either a C 1 -C 10  hydrocarbon group, and a hydroxyl group, an imino group, an imino group substituted by a C 1 -C 10  hydrocarbon group or a hydroxyl group, or oxygen, h is equal to 1 if e=1 and equal to 0 or 1 if e=2, with the proviso that the group—N—(X) e  in formula (1a) is replaced by a group represented by formula (5a′) below if h=0;  
 said formula (5a′) being represented by  
                 
 
 wherein the N corresponds to the N in formula (1a) and R 19 -R 22  and Y are as defined in formula (5a).  
 
 
   
     
     
         2 . The gasoline additive according to    claim 1    wherein said component (1A) is represented by the formula  
                 

 wherein R 1  is selected from the group consisting of a hydrogen, a C 1 -C 12  alkyl group, a C 6 -C 18  aryl or alkylaryl group, R 2 , R 3 , R 4  and R 5  are each independently selected from the group consisting of a hydrogen, a C 1 -C 8  alkyl group, and a group of formula (2a), a is an integer from 2 to 200, R 6  is a C 1 -C 6  alkylene group, b is 0 or 1, Z is a group selected from Group A below, c is either 0 or 1, X is a group selected from Group B below, d is either 1 or 2, e is either 1 or 2 and the sum of d and e is equal to 3,  
 said formula (2a) being represented by  
                 
 
 wherein R 7  and R 8  are each independently selected from the group consisting of a hydrogen, a C 1 -C 6  alkyl group, and a C 2 -C 6  alkoxyalkyl group, R 9  is either a C 2 -C 6  alkylene group or a C 2 -C 8  ethylene group having an alkoxyalkyl substituent, R 10  is a C 1 -C 24  alkyl group, and f is an integer from 0 to 30, said Group A being constituted by 
 (A1) —O—CO—,  
 (A2) —CO—, and  
 (A3) —O—CO—R 11 —
 wherein R 11  is a C 1 -C 4  alkylene group  
 
 (A4) —O—CO—O—R 12  
 wherein R 12  is a C 1 -C 4  alkylene group,  
 
 (A5) —CO—O—R 13 —
 wherein R 13  is a C 1 -C 4  alkylene group  
 
 and  
 
 said Group B being constituted by 
 (B1) hydrogen,  
 (B2) a C 1 -C 12 alkyl group or a C 6 -C 12  aryl or arylalkyl group  
 (B3) an alkanol group represented by the formula 
 —R 14 —OH  (3a) wherein R 14  is a C 1 -C 4  alkylene group,    
 (B4) a nitrogen-containing group represented by the formula  
                 

 wherein R 15  is a C 2 -C 4  alkylene group, R 16  is selected from the group consisting of a hydrogen, a C 1 -C 3  alkyl group, and a group of formula (3a), R 17  is selected from the group consisting of a hydrogen, a C 1 -C 12  alkyl group, a C 6 -C 12  aryl or arylalkyl group, and a group of formula (3a), and g is an integer from 1 to 4, and  
 
 (B5) a group represented by the formula  
                 

 wherein R 18  is a C 2 -C 4  alkylene group, R 19 , R 20 , R 21  and R 22  are each independently selected from the group consisting of hydrogen, a C 1 -C 6  alkyl group, and a hydroxyl group, Y is selected from the group consisting of a methylene group, a methylene group substituted by a C 1 -C 6  alkyl group or a hydroxyl group, an imino group, an imino group substituted by a C 1 -C 6  alkyl group or a hydroxyl group, and oxygen, h is equal to 1 if e=1 and equal to 0 or 1 if e=2, with the proviso that the group —N—(X) e  in formula (1a) is replaced by a group represented by formula (5a′) below if h=0; said formula (5a′) being represented by  
                 
 
 wherein the N corresponds to the N in formula (1a) and R 19 -R 22  and Y are as defined in formula (5a).  
 
 
 
     
     
         3 . The gasoline additive according to    claim 1    wherein said component (1A) is represented by the formula  
                 

 wherein R 1  is selected from the group consisting of a hydrogen or a C 1 -C 6  alkyl group, a phenyl group, and a C 7 -C 15  alkylaryl group, and wherein R 2 , R 3 , R 4  and R 5  are each independently selected from the group consisting of a hydrogen, a C 1 -C 3  alkyl group and a group of formula (2a) below, a is an integer from 2 to 100, R 6  is a C 3 -C 6  alkylene group, b is either 0 or 1, Z is a group selected from Group A below, c is either 0 or 1, X is a group selected from Group B below, d is 1, e is 2, and  
 said formula (2a) being represented by  
                 
 
 wherein R 7  and R 8  are each independently selected from the group consisting of a hydrogen and a C 1 -C 3  alkyl group, R 9  is a C 2 -C 4  alkylene group, R 10  is a C 1 -C 12  alkyl group, and f is an integer from 0 to 20,  
 said Group A being constituted by 
 (A1) —O—CO—,  
 (A2) —CO—, and  
 (A4) —O—CO—O—R 12 —
 wherein R 12  is a C 1 -C 4  alkylene group, and  
 
 said Group B being constituted by 
 (B1) hydrogen,  
 (B3) an alkanol group represented by the formula 
 —R 14 —OH  (3a) wherein R 14  is a C 1 -C 3  alkylene group,    
 (B4) a nitrogen-containing group represented by the formula  
                 

 wherein R 15  is a C 2 -C 3  alkylene group, R 16  is selected from the group consisting of a hydrogen, a methyl group, an ethyl group, and a group of formula (3a), R 17  is selected from the group consisting of a hydrogen, a C 1 -C 6  alkyl group, a phenyl group, a C 7 -C 9  arylalkyl group and a group of formula (3a), and g is an integer from 1 to 3, and  
 
 (B5) a group represented by the formula  
                 

 wherein R 18  is a C 2 -C 3  alkylene group, R 19 , R 20 , R 21  and R 22  are each independently selected from the group consisting of a hydrogen, a C 1 -C 3  alkyl group and a hydroxyl group, Y is selected from the group consisting of an imino group, an imino group substituted by a C 1 -C 3  alkyl group or a hydroxyl group and oxygen, h is equal to 0 or 1, with the proviso that with the group —N—(X) e  in formula (1a) is replaced by a group represented by formula (5a′) below if h=0;  
 said formula (5a′) being represented by  
                 
 
 wherein the N corresponds to the N in formula (1a) and R 19 -R 22  and Y are as defined in formula (5a).  
 
 
 
 
     
     
         4 . The gasoline additive according to    claim 1    wherein said polybutenylamine compound is a compound (1B) represented by the formula  
                 

 wherein R 25  is selected from the group consisting of an n-butyl group, a sec-butyl group, and a tert-butyl group, R 26 , R 27 , R 28  and R 29  are each independently a hydrogen, a methyl group and an ethyl group, and the total carbon number of R 26 , R 27 , R 28  and R 29  groups is 2, Q is a group represented by one of formulae (2b) to (7b) below, R 30  and R 31  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  hydrocarbon group, a C 1 -C 8  alkanol group, and a group represented by formula (8b) below, and m is an integer from 1 to 100,  
 said formulae (2b) to (7b) being represented by  
                 
 
 said formula (8b) being represented by  
                 
 
 wherein R 32  is a C 1 -C 4  alkylene group, R 33  is either a hydrogen or a C 1 -C 4  alkyl group, R 34  is either a hydrogen or a C 1 -C 10  hydrocarbon group, and n is an integer from 1 to 5.  
 
     
     
         5 . The gasoline additive according to    claim 4    wherein said compound (1B) is represented by the formula  
                 

 wherein either (i) R 25  is a tert-butyl group, R 26  and R 28  are each hydrogen and R 27  and R 29  are each a methyl group, or (ii) R 25  is a tert-butyl group, R 26  and R 28  are each a methyl group and R 27  and R 29  are each hydrogen, Q is a group represented by formula (2b) or (6b) below, R 30  and R 31  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  alkyl group, a C 2 -C 10  alkenyl group, a C 5 -C 10  cycloalkyl or alkylcycloalkyl group, a C 6 -C 10  aryl or alkylaryl group, a C 7 -C 10  arylalkyl group, a C 1 -C 8  alkanol group, and a group represented by formula (8b) below, and m is an integer from 5 to 50,  
 said formulae (2b) and (6b) being represented by  
                 
 
 said formula (8b) being represented by  
                 
 
 wherein R 32  is a C 1 -C 3  alkylene group, R 33  is either hydrogen or a C 1 -C 3  alkyl group, R 34  is either hydrogen or a C 1 -C 3  alkyl group, and n is an integer from 1 to 3.  
 
     
     
         6 . The gasoline additive according to    claim 4    wherein said compound (1B) is represented by the formula  
                 

 wherein either (i) R 25  is tert-butyl group, R 26  and R 28  are each hydrogen and R 27  and R 29  are each methyl group or (ii) R 25  is tert-butyl group, R 26  and R 28  are each methyl group and R 27  and R 29  are each a hydrogen atom, Q is a group represented by formula (6b), R 30  and R 31  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  alkyl group, a C 2 -C 10  alkenyl group, a C 5 -C 10  cycloalkyl or alkylcycloalkyl group, a C 6 -C 10  aryl or alkylaryl group, a C 7 -C 10  arylalkyl group, a C 1 -C 4  alkanol group, and a group represented by formula (8b) below and m is an integer from 10 to 40,  
 said formulae (6b) being represented by  
                 
 
 said formula (8b) being represented by  
                 
 
 wherein R 32  is a C 1 -C 3  alkylene group, R 33  and R 34  is each a hydrogen, and n is an integer of 1.  
 
     
     
         7 . The gasoline additive according to    claim 4    wherein the number-average molecular weight of said compound (1B) is within the range of 200 to 6,000.  
     
     
         8 . The gasoline additive according to    claim 4    wherein the number-average molecular weight of said compound (1B) is within the range of 400 to 3,000.  
     
     
         9 . The gasoline additive according to    claim 4    wherein the number-average molecular weight of said compound (1B) is within the range of 700 to 2,400.  
     
     
         10 . A gasoline composition for use in a direct injection gasoline engine, which composition comprises a base gasoline and at least one nitrogen-containing compound selected from the group consisting of compound (1A) and a polybutenylamine compound: 
 said compound (1A) being represented by the formula  
                 
   wherein R 1  is either a hydrogen or a C 1 -C 30  hydrocarbon group, R 2 , R 3 , R 4  and R 5  are each independently selected from the group consisting of a hydrogen, a C 1 -C 16  hydrocarbon group, and a group of formula (2a) below, a is an integer from 1 to 200, R 6  is a C 1 -C 10  hydrocarbon group, b is either 0 or 1, Z is a group selected from Group A below, c is either 0 or 1, X is a group selected from Group B below, d is an integer from 1 to 3, e is an integer from 0 to 2, and the sum of d and e is equal to 3,    said formula (2a) being  
                 
   wherein R 7  and R 8  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  hydrocarbon group and a C 2 -C 10  alkoxyalkyl group, R 9  is either a C 2 -C 6  alkylene group or a C 4 -C 10  alkylene group having an alkoxyalkyl substituent, R 10  is a C 1 -C 30  hydrocarbon group, and f is an integer from 0 to 50,    said Group A being constituted by 
 (A1) —O—CO— 
 (A2) —CO— 
 (A3) —O—CO—R 11 —
 wherein R 11  is a C 1 -C 6  alkylene group,  
 
 (A4) —O—CO—O—R 12 —
 wherein R 12  is a C 1 -C 6  alkylene group, and  
 
 (A5) —CO—O—R 13 —
 wherein R 13  is a C 1 -C 6  alkylene group,  
 
 said Group B being constituted by 
 (B1) hydrogen,  
 (B2) a C 1 -C 30  hydrocarbon group,  
 (B3) an alkanol group represented by the formula 
 —R 14 —OH  (3a) wherein R 14  is a C 1 -C 6  alkylene group,    
 (B4) a nitrogen-containing group represented by the formula  
                 

 wherein R 15  is a C 2 -C 6  alkylene group, R 16  is selected from the group consisting of a hydrogen, a C 1 -C 4  alkyl group and a group of formula (3a), R 17  is selected from the group consisting of a hydrogen, a C 1 -C 30  hydrocarbon group, and a group of formula (3a), and g is an integer of between 1 and 5, and  
 
 (B5) a group represented by the formula  
                 

 wherein R 18  is a C 2 -C 6  alkylene group, R 19 , R 20 , R 21  and R 22  are each independently selected from the group consisting of a hydrogen, a C 1 -C 10  hydrocarbon group, and a hydroxyl group, Y is selected from the group consisting of a methylene group, a methylene group substituted by a C 1 -C 10  hydrocarbon group or a hydroxyl group, an imino group, an imino group substituted by a C 1 -C 10  hydrocarbon group or a hydroxyl group, and oxygen, h is equal to 1 if e=1 and equal to 0 or 1 if e=2, with the proviso that the group —N—(X) e  in formula (1a) is replaced by a group represented by formula (5a′) below if h=0;  
 said formula (5a′) being represented by  
                 
 
 wherein the N corresponds to the N in formula (1a) and R 19 -R 22  and Y are as defined in formula (5a).  
 
 
   
     
     
         11 . The gasoline composition according to    claim 10    wherein said compound (1A) is contained in an amount of 0.001 to 10 mass percent, based on the total composition.  
     
     
         12 . The gasoline composition according to    claim 10    wherein said polybutenylamine compound is contained in an amount of 0.001 to 10 mass percent, based on the total composition.