A new polyhydrocarbon-polyamine AB block copolymer

Copolymers of ethylene and 1-butene were synthesized using a single-site zi rconium-based coordination catalyst. The polymers terminated exclusively in 1-butene ends, predominantly ethylvinylidene. They were carbonylated under Koch-Haaf conditions using boron trifluoride, carbon monoxide, and phenols to give polymeric hydrocarbons containing a single carboaryloxy group. Bot h 1,3- and 1,5-rearrangements were observed in this synthesis. The aminatio n reaction with polyethylene amines followed second-order kinetics, but wit h a steadily decreasing bimolecular rate constant. The physical properties along with the block composition of the resulting polyhydrocarbon polyamine make this a potential candidate for motor oil dispersant. To interpret the polymer results, appropriate model compounds consisting of appropriately b ranched carboxylic acids, aryl eaters, and amides were synthesized. The C-1 3 NMR and IR spectra, both of the quaternary carbons and the carbonyls, sup ported the structure assignment for the polymers. Finally, the kinetics of the reactions of the model esters with model monoamines N,N-dimethyltrimeth ylenediamine and N-2-(ethylamino)piperidine quantitatively reproduced the a midation kinetics observed for the polymeric ester.