Method For Producing Polyolefinic Amines and compositions Containing Same

Abstract

Polyolefinic amines may be produced in a reaction comprising contacting an olefin or a polyolefin with an azo compound under free radical conditions to form a polyolefinic nitrile having an average molecular weight of at least 250, followed by reducing the polyolefinic nitrile to a corresponding polyolefinic amine. The polyolefinic amines produced by the reaction may be included as a detergent in compositions, such as fuel compositions, additive compositions, and/or carrier compositions.

1 . A reaction, comprising contacting an olefin or a polyolefin with an azo compound under free radical conditions to form a polyolefinic nitrile having an average molecular weight of at least 250. 
     
     
         2 . The reaction of  claim 1 , wherein the azo compound is selected from the group consisting of 2,2′-azobisisobutyronitrile (“AIBN”), 2,2′-azobis(2-butanenitrile), 1,1′-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2cyanopropane, 2,2′-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2hydroxyethyl]-propionamide, 2,2′-azobis(2-methyl-Nhydroxyethyl)propionamide, 2,2′-azobis(N,N′-dimethyleneisobutyramidine)dichloride, 2,2′-azobis(2amidinopropane)dichloride, 2,2′-azobis(N,N′dimethyleneisobutyramide), 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)2-hydroxyethyl]propionamide), 2,2′-azobis(2-methylN-[1,1bis(hydroxymethyl)ethyl]propionamide), 2,2′-azobis(2-methylN-(2-hydroxyethyl)propionamide), 2,2′-azobis(isobutyramide)dihydrate, azobutyronitrile, 2,2′-azobis-(4-methoxy-2,4dimethylpentanenitrile), 2,2′-azobis-(2,4-dimethylpentanenitrile), 2,2′azobis-(2-methylbutyronitrile), 2,2′azobis-(4-methoxy-2,4dimethylvaleronitrile). 
     
     
         3 . The reaction of  claim 2 , wherein the azo compound is 2,2′-azobisisobutyronitrile. 
     
     
         4 . The reaction of  claim 1 , wherein the olefin is an one or more olefins selected from the group consisting of propene, butene, pentene, isobutene, styrene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, hexadecene, tetradecene, pentadecene, heptadecene, nonadecene, octadecene, 1-octadecene, eicocene 1-eicocene, 1-doeicocene, 1-tetraeicocene, 1-hexaeicocene, 1-octaeicocene, 1-triacontene. 
     
     
         5 . The reaction of  claim 1 , wherein the olefin is a mixture of olefins comprising blends of olefins selected from the group consisting of 1-octadecene/1-tetraeicocene, 1-eicocene/1-doeicocene/1-tetraeicocene, and 1-tetraeicocene/1-hexaeicocene/1-octaeicocene. 
     
     
         6 . The reaction of  claim 1 , wherein the polyolefin is one or more polyolefins selected from the group consisting of polypropene, polybutene, polypentene, polyisobutene, polystyrene, polyhexene, polyheptene, polyoctene, polynonene, polydecene, polyandecene, polydodecene, polytridecene, polyhexadecene, polytetradecene, polypentadecene, polyheptadecene, polynonadecene, polyoctadecene, polyeicocene. 
     
     
         7 . The reaction of  claim 6 , wherein the polyolefin is polyisobutene. 
     
     
         8 . The reaction of  claim 1 , wherein the reaction further comprises a catalyst that facilitates the reaction between the olefin or the polyolefin and the azo compound. 
     
     
         9 . The reaction of  claim 8 , wherein said catalyst that facilitates the reaction between the olefin or the polyolefin and the azo compound is a naked cation catalyst. 
     
     
         10 . The reaction of  claim 8 , wherein said catalyst that facilitates the reaction between the olefin or the polyolefin and the azo compound is selected from the group consisting of boranes, carboranes, fullerides, metallocenes, and lithium containing catalysts. 
     
     
         11 . The reaction of  claim 10 , wherein said lithium containing catalyst is a weakly solvated lithium cation. 
     
     
         12 . The reaction of  claim 10 , wherein said lithium containing catalyst is LiCB 11 (CH 3 ) 2 . 
     
     
         13 . The reaction of  claim 1 , further comprising reducing said polyolefinic nitrile to a corresponding polyolefinic amine. 
     
     
         14 . The reaction of  claim 13 , wherein reducing said polyolefinic nitrile to a corresponding polyolefinic amine occurs in the presence of a hydrogenation catalyst. 
     
     
         15 . The reaction of  claim 14 , wherein said hydrogenation catalyst is selected from a group consisting of Raney nickel, palladium, platinum, cobalt, copper, copper oxide, Lindlar catalyst, rhodium, platinum dioxide, sodium borohydride, nickel, ruthenium, iron, tellurium, copper triphenylphosphine complexes, ruthenium phosphine complexes, rhodium carbonyl clusters, palladium on carbon, and complexes of palladium with quinoline, pyridine, and phenylisocyano ligands. 
     
     
         16 . The reaction of  claim 13 , wherein said polyolefinic amine contains an average number of carbon atoms of at least about 12. 
     
     
         17 . The reaction of  claim 13 , wherein said polyolefinic amine contains greater than about 35%, by weight of total polyolefin amine molecules, polyolefin amine molecules with at least 12 carbon atoms. 
     
     
         18 . The reaction of  claim 13 , wherein said polyolefinic amine is a mixture in which the predominant polyolefin amine molecule contains at least about 12 carbon atoms per molecule. 
     
     
         19 . A composition comprising polyolefinic amines produced by the reaction of  claim 13 . 
     
     
         20 . The composition of  claim 19 , wherein the composition additionally contains one or more additives selected from the group consisting of combustion improvers, cetane improvers, friction modifiers, detergents, dispersants, antioxidants, heat stabilizers, corrosion inhibitors, dehazers, metal deactivators, antifoaming agents, cosolvents, package compatibilisers, lubricity additives, antistatic additives, scavengers, pollution suppressants, cold flow improvers, and demulsifiers. 
     
     
         21 . A fuel composition comprising polyolefinic amines produced by the reaction of  claim 13  in a minor amount and a major amount of a hydrocarbon fuel. 
     
     
         22 . The fuel composition of  claim 21 , wherein said polyolefinic amines produced by the reaction of  claim 13  are present in an amount that is about 10 to about 10,000 parts per million. 
     
     
         23 . The fuel composition of  claim 22 , wherein said fuel composition additionally contains one or more additives selected from the group consisting of combustion improvers, cetane improvers, friction modifiers, detergents, dispersants, antioxidants, heat stabilizers, corrosion inhibitors, dehazers, metal deactivators, antifoaming agents, cosolvents, package compatibilisers, lubricity additives, antistatic additives, scavengers, pollution suppressants, cold flow improvers, and demulsifiers. 
     
     
         24 . A method for improving detergency comprising providing a composition that comprises polyolefinic amines produced by the reaction of  claim 13 . 
     
     
         25 . A method of preventing deposits in an engine comprising contacting the engine with a composition that comprises polyolefinic amines produced by the reaction of  claim 13 . 
     
     
         26 . A use of a composition comprising polyolefinic amines produced by the reaction of  claim 13 . 
     
     
         27 . An engine comprising polyolefinic amines produced by the reaction of  claim 13 .