Characteristic System Time Scales Can Influence the Collective Sequence Development of Nematically Ordered Copolymers.

The sequence of copolymers is of significant importance to their material properties, yet controlling the copolymer sequence remains a challenge. Previously, we have shown that polymer chains with sufficient stiffness and intermolecular attractions can undergo an emergent, polymerization-driven nematic alignment of nascent oligomers during a step-growth polymerization process. Both the extent of alignment and the point in the reaction at which it occurs impact the kinetics and the sequence development of the growing polymer. Of particular interest is the emergence of a characteristic block length in the ensemble of sequences, resulting in unusually peaked block length distributions. Here we explore the emergence of this characteristic block length over time and investigate how changes in activation energy, solution viscosity, and monomer density influence the sequence and block length distributions of stiff copolymers undergoing step-growth polymerization. We find that emergent aggregation and nematic ordering restrict the availability of longer chains to form bonds, thereby altering the propensity of chains to react in a length dependent fashion, which changes as the reaction progresses, and promoting the formation of chains and blocks of a characteristic length. Further, we demonstrate that the characteristic length scale which emerges is sensitive to the relative time scales of reaction kinetics and reactant diffusion, shifting in response to changes in the activation energy of the reaction and the viscosity of the solvent. Our observations suggest the potential for biasing characteristic lengths of sequence repeats in stiff and semiflexible copolymer systems by targeting specific nonbonded interactions and reaction kinetics through the informed adjustment of reaction conditions and the selection or chemical modification of monomer species.