Computational Investigation of the Effect of Network Architecture on Mechanical Properties of Dynamically Cross‐Linked Polymer Materials

Abstract

Dynamically cross‐linked polymer networks have attracted significant interest in recent years due to their unique and improved properties including increased toughness, malleability, shape memory, and self‐healing. Here, a computational study on the mechanical behavior of dynamically cross‐linked polymer networks is presented. Coarse grained models for different polymer network configurations are established and their mechanical properties using molecular dynamics (MD) simulations are predicted. Consistent with the experimental measurements, the simulation results show that interpenetrating networks (IPN) withstand considerably higher stress compared to the single networks (SN). Additionally, the MD results demonstrate that the origin of this variation in mechanical behavior of IPN and SN configurations goes back to the difference in spatial degrees of freedom of the noncovalent cross‐linkers, represented by nonbonded interactions within the two system types. The results of this work provide new insight for future studies on the design of systems with dual dynamic cross‐linkers where one linkage exchanges rapidly and provides autonomic dynamic character, while the other is a stimulus responsive dynamic covalent linkage that provides stability with dynamic exchange on‐demand.

Complementary Dynamic Chemistries for Multifunctional Polymeric Materials

“…Since the H‐bonds are in their own network, they are free to rearrange in the IPN allowing more DNCBs to associate in the less restricted IPN architecture. [ 142 ]…”

Carbon nanotube enhanced dynamic polymeric materials through macromolecular engineering

“…MD simulations were used to evaluate the mechanical properties of the polymer matrix, the polymer matrix with nanotubes, and the matrix with covalent bonds between the nanotubes and the matrix. A coarse-grained model for the polymers and cross-linkers 34 was used with polymer chains made up of 100 beads, interconnected through covalently bonded furan-maleimide crosslinkers. There are 7 linkers introduced per polymer chain to represent the 7% cross-linkers present in the experimental setup.…”

“…The crosslinker was based on furan-maleimide DA adducts developed earlier. 34 The simulation approach and a snapshot from the simulation are presented in Fig. S19 (ESI †).…”

Mapping crosslinking reaction–structure–property relationship in polyether‐based vinylogous urethane vitrimers

“…Undoubtedly, a synergy between computer simulation/semi‐empirical model interpretation and experiments is capable of providing invaluable structural information at molecular level and thus being linked to their properties 40–44 . As a pivotal structural parameter, crosslinking density is closely related to the thermomechanical and the viscoelastic properties of vitrimers.…”