Complex patterns integral to the structure and function of biological materials arise spontaneously during morphogenesis. In contrast, functional patterns in synthetic materials are typically created through multistep manufacturing processes, limiting accessibility to spatially varying materials systems. Here, we harness rapid reaction-thermal transport during frontal polymerization to drive the emergence of spatially varying patterns during the synthesis of engineering polymers. Tuning of the reaction kinetics and thermal transport enables internal feedback control over thermal gradients to spontaneously pattern morphological, chemical, optical, and mechanical properties of structural materials. We achieve patterned regions with two orders of magnitude change in modulus in poly­(cyclooctadiene) and 20 °C change in glass transition temperature in poly­(dicyclopentadiene). Our results suggest a facile route to patterned structural materials with complex microstructures without the need for masks, molds, or printers utilized in conventional manufacturing. Moreover, we envision that more sophisticated control of reaction-transport driven fronts may enable spontaneous growth of structures and patterns in synthetic materials, inaccessible by traditional manufacturing approaches.

Dynamic networks with precise spacers between boronic ester bonds were investigated over a broad temperature window. Arrhenius behavior breaks down and an increase in relaxation time is observed when approach the glass transition temperature.

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.