Abstract
AbstractSummary: The preparation of polystyrene block methyl methacrylate copolymers (PS‐b‐PMMA) is described. The polystyrene segment was prepared by anionic polymerization and the methylmethacrylate segment was prepared via free radical autoxidation of a borane agent attached to the styrene chain.1 The chemistry involves a transformation of the anionic polymerization process to borane chemistry by firstly producing polystyrene with chain end unsaturated alkyl functional groups prepared using a n‐butyllithium initiator and termination with allylchlorodimethylsilane. Secondly, the unsaturated macroinitiator end was hydroborated by 9‐borabicyclo[3.3.1]nonane (9‐BBN) to produce a borane terminated PS. Thirdly, the borane group at the chain end was selectively oxidized and converted to polymeric radicals in the presence of methyl methacrylate which then initiated radical polymerization to produce block copolymers. The polymer obtained was characterized using several chromatographic techniques including LC‐CC (liquid chromatography under critical conditions) for the polystyrene segments and two‐dimensional chromatography with LC‐CC in the first dimension and SEC in the second. The results show that block formation was successful although significant homopolymerization of methyl methacrylate is also obtained.
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