Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets

TLDR

The traditional distinction between thermoplastics and thermosets is blurred by covalent adaptable networks (CANs) that incorporate dynamic crosslinks, allowing materials to act as both robust networks and moldable plastics. This Perspective outlines the theory of CANs, evaluates their current status, and proposes solutions to advance fundamental understanding. CAN properties arise from network chemistry, especially the dissociative or associative crosslink exchange mechanisms activated by heat, which govern material behavior during processing.

Abstract

The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct and irreconcilable. Yet, the past two decades have seen extensive development of materials that bridge this gap through incorporation of dynamic crosslinks, enabling them to behave as both robust networks and moldable plastics. Although their potential utility is significant, the growth of covalent adaptable networks (CANs) has obscured the line between "thermoplastic" and "thermoset" and erected a conceptual barrier to the growing number of new researchers entering this discipline. This Perspective aims to both outline the fundamental theory of CANs and provide a critical assessment of their current status. We emphasize throughout that the unique properties of CANs emerge from the network chemistry, and particularly highlight the role that the crosslink exchange mechanism (i.e., dissociative exchange or associative exchange) plays in the resultant material properties under processing conditions. Predominant focus will be on thermally induced dynamic behavior, as the majority of presently employed exchange chemistries rely on thermal stimulus, and it is simple to apply to bulk materials. Lastly, this Perspective aims to identify current issues and address possible solutions for better fundamental understanding within this field.