The synthesis of unique polymers with star-shaped molecular bottlebrush topology is reported. Macromolecules were prepared by the combination of bottlebrush arms with a molecular spoked wheel (MSW) core. A hexahydroxy-functionalized MSW was synthesized and converted into six-fold ATRP initiator (6-Br), from which six backbone arms with HEMA-TMS units were grafted via Atom Transfer Radical Polymerization (ATRP). Post-functionalization of the polymers provided star-shaped ATRP macroinitiators, which were further used to polymerize side chains by ATRP, thus producing star-shaped bottlebrush architectures. Three different hexa-armed brush copolymers with varying lengths of arms and grafts, i. e. MSW(420-g-20)6, MSW(420-g-40)6 and MSW(200-g-60)6, were prepared. GPC confirmed the formation of well-defined structures with narrow molecular weight distributions and AFM allowed for the visualization of individual polymers with unique starfish topology. Additionally, an intriguing aggregation behavior of the star-shaped macroinitiators and cleavage of star arms due to high congestion were observed.

Synthesis of star-shaped bottlebrushes with molecular spoked wheel core

248th National Meeting (2014)

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