Going Beyond the Carothers, Flory and Stockmayer Equation by Including Cyclization Reactions and Mobility Constraints.

ABSTRACT: A challenge in the field of polymer network synthesis by a step-growth mechanism is the quantification of the relative importance of inter- vs. intramolecular reactions. Here we use a matrix-based kinetic Monte Carlo (kMC) framework to demonstrate that the variation of the chain length distribution and its averages (e.g., number average chain length x_n), are largely affected by intramolecular reactions, as mostly ignored in theoretical studies. We showcase that a conventional approach based on equations derived by Carothers, Flory and Stockmayer, assuming constant reactivities and ignoring intramolecular reactions, is very approximate, and the use of asymptotic limits is biased. Intramolecular reactions stretch the functional group (FG) conversion range and reduce

SUBMITTER: De Keer L 

PROVIDER: S-EPMC8348631 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature