Living anionic polymerization plays an important role in the synthesis of well-defined macromolecules, especially with regard to block copolymers and terminally functionalized polymers. This work describes on the one hand how to adjust the reactivity to guarantee quantitative functionalization of poly(2-vinylpyridine) (P2VP) and poly(ferrocenyldimethylsilane) (PFDMS) with functional epoxide derivatives and on the other hand the monomer sequence distribution monitoring in living carbanionic copolymerization by real-time 1H NMR spectroscopy.Both polymers, P2VP and PFDMS, are stimuli responsive. At a pH value below 4.8 a sufficient number of pyridine rings get protonated to render P2VP water-soluble, whereas PFDMS is redox active and has unique aggregation properties in bulk and solution. However both living polymers cannot be terminated directly with epoxides but by adjusting the reactivity of the propagating specie this throwbacks can be solved.Direct carbanionic copolymerization represents an almost neglected field in recent decades, although control of the monomer sequence distribution within the resulting polymer chains is of growing interest. In our contribution we focus on in situ monitoring of living carbanionic copolymerizations to study the evolution of the comonomer sequence in great detail to improve the understanding of monomer sequence distribution. Two different comonomer pairs have been investigated, the chemically similarly protected poly(p-hydroxystyrene) (PpHS) derivatives, p(1-ethoxy ethoxy)styrene (pEES) and 4-tert-butoxystyrene (tBuOS) as well as styrene (S) and pEES, which differ in their reactivity.

Solving modern problems in carbanionic polymerization: Termination and sequence control

247th National Meeting (2014)

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