A multi‐matrix kinetic Monte Carlo framework enabling the design of sequence‐controlled star block copolymers

Abstract Precise tailoring of chemical structures is fundamental to chemical product engineering. Star block copolymers, as advanced branched polymers, possess unique properties deriving from sequence structures. Herein, we propose a multiple matrix‐based kinetic Monte Carlo ( k MC) framework capable of capturing both complex topologies and sequence structures of star block copolymers. This approach employs primary matrices to record the structure of arms and cores, along with submatrices to map connections between each arm and its corresponding core. By integrating this k MC algorithm with the recently developed sequence structure descriptor, we simulate the atom transfer radical copolymerization of n‐butyl acrylate and styrene to produce sequence‐controlled star block copolymers. Kinetic analysis highlights the importance of the activation/deactivation equilibrium of the first monomer in the two‐step batch copolymerization. Comprehensive optimization across three key conditions enables precise regulation of sequence structures while achieving a balance between time cost and monomer utilization efficiency.