Sequence-Engineering Polyethylene-Polypropylene Copolymers with High Thermal Conductivity Using a Molecular-Dynamics-Based Genetic Algorithm.

Polymer sequence engineering is emerging as a potential tool to modulate material properties. Here, we employ a combination of a genetic algorithm (GA) and atomistic molecular dynamics (MD) simulation to design polyethylene-polypropylene (PE-PP) copolymers with the aim of identifying a specific sequence with high thermal conductivity. PE-PP copolymers with various sequences at the same monomer ratio are found to have a broad distribution of thermal conductivities. This indicates that the monomer sequence has a crucial effect on thermal energy transport of the copolymers. A non-periodic and non-intuitive optimal sequence is indeed identified by the GA, which gives the highest thermal conductivity compared with any regular block copolymers, for example, diblock, triblock, and hexablock. In comparison to the bulk density, chain conformations, and vibrational density of states, the monomer sequence has the strongest impact on the efficiency of thermal energy transport via inter- and intra-molecular interactions. Our work highlights polymer sequence engineering as a promising approach for tuning the thermal conductivity of copolymers, and it provides an example application of integrating atomistic MD modeling with the GA for computational material design.