Dynamics of dual-junction-functionality associative polymer networks with ion and nanoparticle metal-coordinate cross-link junctions

Abstract

We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low functionality ( f) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high- f junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high- f junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high- f) and metal ion (low- f) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high- f networks.