Synthesis of block polymer miktobrushes

Abstract

Well defined mu-A(BC)(n) 'miktobrush' terpolymers were synthesized utilizing the alternating radical copolymerization of two hydrophobic and incompatible macromonomer (MM) building blocks; a maleimide (MI) end functionalized poly(methyl-caprolactone) block (MI-PMCL) or 'C' and a styrene (Sty) end functionalized poly(perfluoro propylene oxide) block (Sty-PFPO) or 'F'. Polymerizations were mediated by a poly(ethylene oxide) (PEO) functionalized reversible addition-fragmentation chain transfer (RAFT) agent (PEO-CTA) or 'O' to control the chain growth of the MMs from the O block to form O(CF)(n) "miktobrush" terpolymers. The synthesis of a range of well defined mu-O(CF)(n) terpolymers with various compositions was achieved by changing the feed of MMs. All building blocks and brush polymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC) and elemental analyses. This new strategy offers a powerful route towards a block polymer architecture that can enable the formation of multi-domain hierarchical nanostructures with features on multiple length scales due to the incompatibility and unique connectivity of the building blocks incorporated.