Reversible stepwise condensation polymerization with cyclization: strictly alternating co-polymerization and homopolymerization based upon two orthogonal reactions

TL;DR

This paper develops a recursive scheme to analyze reversible stepwise condensation polymerization with cyclization, focusing on strictly alternating copolymerization and homopolymerization using two orthogonal reactions, providing analytical and numerical solutions.

Contribution

It introduces a novel recursive approach to treat complex reversible polymerizations with cyclization, including cases not previously addressed in literature.

Findings

Derived analytical expressions for polymer weight distributions.

Provided exact numerical solutions validated by Monte Carlo simulations.

Analyzed effects of cyclization on polymer properties.

Abstract

In a preceding work [M. Lang, K. Kumar, A simple and general approach for reversible condensation polymerization with cyclization, Macromolecules 54 (2021) 7021], we have introduced a simple recursive scheme that allows to treat stepwise linear reversible polymerizations of any kind with cyclization. This approach is used to discuss the polymerization of linear Gaussian strands (LGS) with two different reactive groups $A$ and $B$ on either chain end that participate in two orthogonal reactions and the strictly alternating copolymerization of LGS that carry $A$ reactive groups with LGS equipped with type $B$ reactive groups. The former of these cases has not been discussed theoretically in literature, the latter only regarding some special cases. We provide either analytical expressions or exact numerical solutions for the general cases with and without cyclization. Weight distributions, averages, polydispersity, and the weight fractions of cyclic and linear species are computed. All numerical solutions were tested by Monte-Carlo simulations.