Summary: Although controlled/living radical copolymerization has been extensively studied, the control of copolymer composition distribution receives little attention. In this paper, taking RAFT copolymerization as an example, we develop a mathematical model and simulate copolymerization systems with various reactivity ratios. It is demonstrated that through semi‐batch operations with programmed profiles of slow monomer feeding rate, precise control over copolymer composition distribution (uniform and designed gradient distributions) along polymer chain can be achieved. It is also found that the semi‐batch operations have lower rates of polymerization than their batch counterparts. The reason for this difference is analyzed, and the magnitude depends on the reactivity ratios and targeted copolymer composition. The improvement of the semi‐batch rate by distributing a part of the initiator amount to the monomer feeding tank is found to be minor.
Model‐based design and control over composition distribution of gradient copolymers implemented by semi‐batch operations.
