Molecular Architecture Manipulation in Free Radical Copolymerization: An Advanced Monte Carlo Approach to Screening Copolymer Chains with Various Comonomer Sequence Arrangements

Abstract

A Kinetic Monte Carlo (KMC) simulation approach was adopted in this study to capture evolutionary events in the course of free radical copolymerization, through which batch and starved-feed semibatch processes were compared. The implementation of the KMC code developed in this work: (i) enables satisfactory control of the molecular weight of the copolymer by tracking the profiles of concentrations of macroradicals, monomers, and polymer as well as degree of polymerization, polydispersity, and chain length distribution; (ii) captures the bivariate distribution of chain length and copolymer composition; (iii) comprehensively tracks and analyzes detailed information on the molecular architecture of the growing chains, thus distinguishing between sequence length and polydispersity of chains produced in batch and starved-feed semibatch operations; (iv) makes possible the screening of products, based on such details as the number and weight fractions of products having different comonomer units located at various positions along the copolymer chains. The aforementioned characteristics were achieved by stochastic calculations through code developed in-house. This KMC simulator becomes a very useful tool for the development of tailored copolymers through free radical polymerization, with blocks separated with single units of a different type.