Sequence-controlled proline-based polyacrylamides via RAFT polymerization: Influence of sequence structure on polymers performances

The synthesis of sequence-controlled polymers is an important emerging trend in recent polymer science. However, the relationship between the sequence structure and performance of the polymer was rarely studied. Here, we synthesized a series of sequence-controlled proline-based multi-block copolymers via one-pot iterative RAFT polymerization, it achieved high monomer conversions (> 98%), precise control of molecular weight, and low polydispersity. The relationship studied between the sequence structure of multi-block copolymers and thermoresponsive performance revealed that the LCSTs of these copolymers are sequence dependent, and it can be altered by variation the sequence structure. In addition, temperature-variable H-1 NMR analysis and dissipative particle dynamics (DPD) simulation technique were chosen to further study on the nature of phase transition and the relationship between sequence structure and thermoresponsiveness. Thus, we have demonstrated a concise method to construct sequence-controlled bio-based copolymers with precisely adjustable structures and functions which can be applied to the design of biological and medical materials.