Synthesis and Self-Assembly of Well-Defined Star and Tadpole Homo-/Co-/Terpolymers

Tadpole polymers are excellent candidates to explore how architecture can influence self-assembly because they combine two topologies in the same molecule (ring polymer as the head and linear polymer as the tail). In this work, we synthesize well-defined tadpole homo-/co-/terpolymers derived from the appropriate chemical modification reactions of the corresponding 3-miktoarm star homo-/co-/terpolymers via anionic polymerization, high vacuum techniques, and chlorosilane chemistry in combination with the Glaser coupling reaction. The 3-miktoarm star homo-/co-/terpolymers bear two arms with t-butyl dimethylsiloxypropyl functional end-groups, whereas after deprotection, the omega-hydroxyl chain-ends were modified to alkyne moieties. The dialkyne star polymers in the presence of Cu(I)Br and N,N,N',N '',N ''-pentamethyldiethylenetriamine were then transformed to well-defined tadpole homo-/co-/terpolymers. We employed strongly immiscible blocks to enable characterization using electron microscopy and X-ray scattering to explore how the molecular topology influences the self-assembled bulk-state microdomain morphologies.