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 res...

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

Covalent adaptable networks (CANs) are covalently cross-linked polymers that may be reshaped via cross-linking and/or strand exchange at elevated temperatures. They represent an exciting and rapidly developing frontier in polymer science for their potential as stimuli-responsive materials and to make traditionally nonrecyclable thermosets more sustainable. CANs whose cross-links undergo exchange via associative intermediates rather than dissociating to separate reactive groups are termed vitrimers. Vitrimers were postulated to be an attractive subset of CANs, because associative cross-link exchange mechanisms maintain the original cross-link density of the network throughout the exchange process. As a result, associative CANs demonstrate a gradual, Arrhenius-like reduction in viscosity at elevated temperatures while maintaining mechanical integrity. In contrast, CANs reprocessed by dissociation and reformation of cross-links have been postulated to exhibit a more rapid decrease in viscosity with increasing temperature. Here, we survey the stress relaxation behavior of all dissociative CANs for which variable temperature stress relaxation or viscosity data are reported to date. All exhibit an Arrhenius relationship between temperature and viscosity, as only a small percentage of the cross-links are broken instantaneously under typical reprocessing conditions. As such, dissociative and associative CANs show nearly identical reprocessing behavior over broad temperature ranges typically used for reprocessing. Given that the term vitrimer was coined to highlight an Arrhenius relationship between viscosity and temperature, in analogy to vitreous glasses, we discourage its continued use to describe associative CANs. The realization that the cross-link exchange mechanism does not greatly influence the practical reprocessing behavior of most CANs suggests that exchange chemistries can be considered with fewer constraints, focusing instead on their activation parameters, synthetic convenience, and application-specific considerations.

/pdf/reprocessable-cross-linked-polymer-networks-are-associative-zhmwg77wwz.pdf

Reprocessable Cross-Linked Polymer Networks: Are Associative Exchange Mechanisms Desirable?

Vitrimers undergoing dynamic bond exchange enable reprocessing and recycle of thermosets. However, vitrimers are susceptible to creep, leading to their poor dimensional stability, which limits thei...

Facile Preparation of Polyimine Vitrimers with Enhanced Creep Resistance and Thermal and Mechanical Properties via Metal Coordination

Fabricating a single polymer network with a combination of a multi-shape memory effect (multiple-SME), solid-state plasticity, recyclability and self-healing behavior remains a challenge. We designed imine bond and ionic hydrogen bond dual cross-linked polybutadiene (PB) networks. The resulting PB networks showed a triple-shape memory effect, where imine bonds could be used to fix the permanent shape and ionic hydrogen bonds and glass transition acted as the transition segments for fixing/releasing the temporary shapes. Additionally, the dual dynamic bonds offered PB networks outstanding solid-state plasticity, recyclability and self-healing behavior. This strategy provides some insights for preparing shape memory polymers integrating multiple-SME and multi-functionality.

Recyclable, Self-Healing, Thermadapt Triple-Shape Memory Polymers Based on Dual Dynamic Bonds.

Towards mechanical robust yet self-healing polyurethane elastomers via combination of dynamic main chain and dangling quadruple hydrogen bonds

Tailoring vinylogous urethane chemistry for the cross-linked polybutadiene: Wide freedom design, multiple recycling methods, good shape memory behavior

Covalent adaptable networks (CANs) have various potential applications for their dynamic features benefiting from the existence of dynamic covalent bonds (DCBs). Here we exploit acetoacetyl chemistry to design CANs in which acetoacetyl formed amides (AFAs) act as a type of DCBs. We first illuminate that the transamidation of AFAs is ascribed to a “proton-switch” mechanism via model study and DFT calculations. When such AFA linkages are incorporated into cross-linked polymer networks, the malleability and recyclability are demonstrated. After recycling the polymer networks for three times, there are no significant mechanical changes or degradations observed. The study reveals that the transamidation is an economic and efficient exchange reaction in the preparation of CANs.

Revisiting Acetoacetyl Chemistry to Build Malleable Cross-Linked Polymer Networks via Transamidation

Despite many efforts, there is no versatile way to realize reversible cross-linking for most polymers. Inspired by the abstraction of hydrogen and the iniferter polymerization of benzophenone (BP), we report a versatile approach for building dynamic covalent networks for polymers containing C–H bonds. Under ultraviolet irradiation, BP can effectively abstract the hydrogen from polymers to form dormant diarylsemipinacol (DASP) groups on the polymer chains. Then, the dormant DASP-based linkages can be homolytically cleaved upon heating, after which they generate carbon-centered aliphatic radicals and DASP-based radicals. Therefore, the cross-linked polymer network can rearrange its topology through the dissociation and association of DASP-based linkages, which endow polymer networks with remodeling and self-healing abilities. Given that most commercially available polymers contain aliphatic C–H bonds, this provides a general method for forming thermal reversible cross-linked networks.

Versatile Approach to Building Dynamic Covalent Polymer Networks by Stimulating the Dormant Groups

Exploring multiple functions of diarylsemipinacol linked to the saturated ethylene-propylene elastomer: from the dynamic covalent networks to tailoring its macroscopic performance

Inhomogeneities are responsible for the poor mechanical properties of hydrogels. To achieve good performances, this study reports here the design and synthesis of hydrogels with negligible defects named as initiator-crosslinker (IC) hydrogel where hybranched polyether amine (hPEA) performs as both coinitiator and crosslinker. The initiation mechanism used in this system is classical but the crosslinking mechanism is different from the conventional hydrogels. A series of hydrogels with various mechanical properties are synthesized by varying the content ratio of coinitiator hPEA and initiator ammonium persulfate. Tensile tests demonstrated that IC hydrogels had excellent mechanical properties elongation at break up to 3000%. The toughness calculated from stress–strain curve highly depended on the content of hPEA and the largest one is about 4.02 MJ m−3 which is much higher than the conventional hydrogels (0.03 MJ m−3). Rheological and swelling results also indicated the obtained hydrogels are indeed crosslinked by both chemical bond and physical interaction.

Zhiyong Liu

Papers

Tailoring vinylogous urethane chemistry for the cross-linked polybutadiene: Wide freedom design, multiple recycling methods, good shape memory behavior

Revisiting Acetoacetyl Chemistry to Build Malleable Cross-Linked Polymer Networks via Transamidation

Versatile Approach to Building Dynamic Covalent Polymer Networks by Stimulating the Dormant Groups

Exploring multiple functions of diarylsemipinacol linked to the saturated ethylene-propylene elastomer: from the dynamic covalent networks to tailoring its macroscopic performance

A Facile Method Synthesizing Hydrogel Using Hybranched Polyether Amine (hPEA) as Coinitiator and Crosslinker