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 has been adopted in this study to capture evolutionary events in the course of free radical copolymerization, through which batch and starved‐feed semibatch processes are 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 are 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.

Intelligent Monte Carlo: A New Paradigm for Inverse Polymerization Engineering

“…We previously developed a KMC methodology for simulating copolymerization kinetics and microstructure of the virtually synthesized macromolecules within a relatively large simulation volume. [15,18,19,21,25,28,[35][36][37][38] In this work, complex OBCs produced by chain shuttling coordination copolymerization reactions have been selected to demonstrate the capabilities of the enhanced IMC approach. OBC copolymerization reactions possess diverse compositional, segmental (hard/soft), molecular, and microstructural properties.…”

Visualization of Bivariate Sequence Length–Chain Length Distribution in Free Radical Copolymerization

“…In previous work, we described the procedure by which placement of M2 comonomer was monitored . The computational algorithm developed in this work addresses the need for monitoring the length and position of sequences of both monomer types, as demonstrated in Scheme .…”

“…In a previous work, we developed a KMC algorithm to capture the bivariate distribution of chain length and copolymer composition . The algorithm affords the detection of any single growing chain in the polymerization system and can precisely categorize chains according to the number, weight, and position of comonomer units randomly positioned in copolymer chains.…”

Heuristic Search Strategy for Transforming Microstructural Patterns to Optimal Copolymerization Recipes

“…Manipulation and fine‐tuning of copolymer properties has so far been realized mostly through detailed mathematical modeling for the simultaneous regulation of microstructural features of copolymer chains (monomer sequences/arrangements and chain length); see, for instance, refs. . Understanding the microstructure–property relationships in copolymerization is a rather cumbersome activity, and this arises mainly due to the complexity of the macromolecular reactions.…”

“…DOI: 10.1002/mats.201700088 copolymer chains (monomer sequences/ arrangements and chain length); see, for instance, refs. [1][2][3][4][5]. Understanding the microstructure-property relationships in copolymerization is a rather cumbersome activity, and this arises mainly due to the complexity of the macromolecular reactions.…”