Vitrimers: Using Dynamic Associative Bonds to Control Viscoelasticity, Assembly, and Functionality in Polymer Networks.

Vitrimers have been investigated in the past decade for their promise as recyclable, reprocessable, and self-healing materials. In this Viewpoint, we focus on some of the key open questions that remain regarding how the molecular-scale chemistry impacts macroscopic physical chemistry. The ability to design temperature-dependent complex viscoelastic spectra with independent control of viscosity and modulus based on knowledge of the dynamic bond and polymer chemistry is first discussed. Next, the role of dynamic covalent chemistry on self-assembly is highlighted in the context of crystallization and nanophase separation. Finally, the ability of dynamic bond exchange to manipulate molecular transport and viscoelasticity is discussed in the context of various applications. Future directions leveraging dynamic covalent chemistry to provide insights regarding fundamental polymer physics as well as imparting functionality into polymers are discussed in all three of these highlighted areas.

Catalyst-Free Dynamic Networks for Recyclable, Self-Healing Solid Polymer Electrolytes.

Polymer networks with dynamic covalent cross-links act as solids but can flow at high temperatures. They have been widely explored as reprocessable and self-healing materials, but their use as solid electrolytes is limited. Here we report poly(ethylene oxide)-based networks with varying amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to understand the impact of a salt on the ion transport and network dynamics. We observed that the conductivity of our dynamic networks reached a maximum of 3.5 × 10-4 S/cm at an optimal LiTFSI concentration. Rheological measurements showed that the amount of LiTFSI significantly affects the mechanical properties, as the shear modulus varies between 1 and 10 MPa and the stress relaxation by 2 orders of magnitude. Additionally, we found that these networks can efficiently dissolve back to pure monomers and heal to recover their conductivity after damage, showing the potential of dynamic networks as sustainable solid electrolytes.