|200. Mannebach, G.; Müller, A.H.E.: Anionic Copolymerization of 5-(N,N-Dialkylamino)isoprenes, Macromolecular Chemistry and Physics 205, 731 (2004)|
|Key words: anionic polymerization, copolymerization, kinetics (polym.), monomers|
The anionic copolymerization of various 5-(N,N-dialkylamino)isoprenes initiated by sec-butyllithium in hexane is investigated. The bulkiness of the alkyl side chains has a strong influence on the copolymerization behavior, monomer reactivity decreasing in the order of alkyl groups methyl > ethyl propyl > isopropyl. Polymer structures vary from nearly block over tapered and gradient to random, depending on the relative reactivities of comonomers. Since the basicity of the tertiary amino groups depends on the nature of the alkyl groups, it is possible to vary the basicity along the polymer backbone by a suitable choice of the comonomers. Copolymerization kinetics do not seem to follow first- or second-order with respect to monomer conversion and they cannot be described using the terminal model.