Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

Controlling monomer sequence in synthetic macromolecules is a major challenge in polymer science and the order of building blocks has already been demonstrated to determine macromolecular folding, self-assembly and fundamental polymer properties. Dispersity is another key parameter in material design, with both low and high dispersity polymers displaying complementary properties and functions. However, synthetic approaches that can simultaneously control both sequence and dispersity remain experimentally unattainable. Here we report a simple, one pot, and rapid synthesis of sequence-controlled multiblocks with on demand control over dispersity while maintaining high livingness, excellent agreement between theoretical and experimental molecular weights and quantitative yields. Key to our approach is the regulation in chain transfer agent activity during controlled radical polymerization that enables the preparation of multiblocks with gradually ascending (Ɖ=1.16 →1.60), descending (Ɖ=1.66 →1.22), alternating low and high dispersity values (Ɖ=1.17 →1.61 →1.24 →1.70 →1.26) or any combination thereof. The enormous potential of our methodology was further demonstrated through the impressive synthesis of highly ordered pentablock, octablock and decablock copolymers yielding the first generation of multiblocks with concurrent control over both sequence and dispersity.