Impact of crosslinker on stereochemistry of a dynamic covalent polymer network: A molecular dynamics simulation

Abstract

We studied the effect of crosslinking density, ϕc, crosslinker length, m, and crosslinker flexibility on endo to exo adduct ratio in Diels–Alder polymer networks. The fraction of endo attachments, ψendo, increased with an increase of ϕc due to suppression of exo adducts at the early time-limiting stage of the network formation, as also observed in our recently published experimental study [1]. Polymer networks formed with flexible crosslinkers demonstrated a linear growth of ψendo with ϕc for all values of m. ψexo of networks with stiff crosslinkers sharply grew in the range of lower ϕc (ϕc<0.6) and plateaued at ϕc>0.6.