Seed Oligomers Regulate Sequence Development through a Templating Effect in Simulated Irreversible Step-growth Copolymerization

The sequence of copolymers determines their material properties, driving significant interest in realizing the control of synthetic copolymer sequences. Templating with pre-formed seeds provides one potential route to efficiently obtain sequence-controlled polymers. However, the complicated interplay between various factors during polymerization requires more study. We previously found that sufficient chain stiffness and interchain attractions could trigger an emergent self-templating effect through the nematic alignment of nascent oligomers. Herein, we probe this templating effect more directly by adding pre-formed seed chains in simulations of irreversible step-growth copolymerization. The results show that the final sequences are influenced by the addition of seed chains, which affects the emergent microphase separation and reaction kinetics. We also find that the final sequences vary with the sequence, length, and intrinsic stiffness of the pre-formed seeds, as well as with the solvent viscosity and the reaction barriers. This work provides insight into the factors influencing seed templating in step-growth copolymerization and highlights a potentially simple and effective route to improve sequence control through the addition of pre-formed seed chains.