Reversible Stepwise Condensation Polymerization with Cyclization: Strictly Alternating Co-polymerization and Homopolymerization Based upon Two Orthogonal Reactions

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.