Temperature-Selective Dual Radical Generation from Alkyl Diiodide: Applications to Synthesis of Asymmetric CABC Multi-Block Copolymers and Their Unique Assembly Structures

Temperature-selective radical generation from a newly designed alkyl diiodide (I−R²−R¹−I) was studied. R¹−I and I−R² had different reactivities for generating alkyl radicals in the presence of a tetraoctylammonium iodide (ONI) catalyst. Taking advantage of the temperature selectivity, we used the alkyl diiodide as a dual initiator in ONI-catalyzed living radical polymerization to uniquely synthesize CABC non-symmetric multi-block copolymers. Because of their non-symmetric structure, CABC multi-block copolymers form unique assemblies, that is, Janus-type particles with hetero-segment coronas and flower-like particles with hetero-segment petals.