One-Pot Synthesis of ABCDE Multiblock Copolymers with Hydrophobic, Hydrophilic, and Semi-Fluorinated Segments

The scope and accessibility of sequence-controlled multiblock copolymers is demonstrated by direct in situ polymerization of hydrophobic, hydrophilic and fluorinated monomers. Key to the success of this strategy is the ability to synthesize ABCDE, EDCBA and EDCBABCDE sequences with high monomer conversions (> 98%) through iterative monomer additions, yielding excellent block purity and low overall molar mass dispersities (D < 1.16). Small-angle X-ray scattering showed that certain sequences can form well-ordered mesostructures. This synthetic approach constitutes a simple and versatile platform for expanding the availability of tailored polymeric materials from readily available monomers.