High molar mass segmented macromolecular architectures by nitroxide mediated polymerisation

A straightforward synthetic pathway based on nitroxide mediated polymerisation (NMP) for the synthesis of a variety of high molar mass segmented copolymers comprising both polystyrene (PS) and polyether segments is reported. First, various precursors such as linear or star-shaped polyether macromonomers, containing either α-methylstyrene or styrene functions at one polymer terminus, as well as PS and polyether macroalkoxyamines bearing either 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (SG1) end-groups, were prepared. In a second step, these prepolymers were used to design different copolymer architectures such as block, graft, star-grafted, toothbrush and palm tree structures, in which PS constituted the backbone and polyether the side chains. Block copolymers were obtained by NMP of styrene initiated with polyether macroalkoxyamines. Copolymerisation of styrene with linear and star-shaped polyether macromonomers by NMP resulted in graft and star-grafted copolymers, respectively. A toothbrush copolymer was produced in a similar way with the exception of the initiator, which was a PS macroalkoxyamine. Likewise, palm tree architectures were obtained by homopolymerising polyether macromonomers initiated by PS macroinitiators. Advanced characterisation of the different polymer structures was performed, including 2D chromatography.