On-Demand Activation of Transesterification by Chemical Amplification in Dynamic Thiol-Ene Photopolymers.

Chemical amplification is a well-established concept in photoresist technology, wherein one photochemical event leads to a cascade of follow-up reactions that facilitate a controlled change in the solubility of a polymer. Herein, we transfer this concept to dynamic polymer networks to liberate both catalyst and functional groups required for bond exchange reactions under UV irradiation. For this, we exploit a photochemically generated acid to catalyse a deprotection reaction of an acid-labile tert-butoxycarbonyl group, which is employed to mask the hydroxy groups of a vinyl monomer. At the same time, the released acid serves as a catalyst for thermo-activated transesterifications between the deprotected hydroxy and ester moieties. Introduced in an orthogonally cured (450 nm) thiol-click photopolymer, this approach allows for a spatio-temporally controlled activation of bond exchange reactions, which is crucial in light of the creep resistance versus reflow ability trade-off of dynamic polymer networks.

Vitrimeric shape memory polymer-based fingertips for adaptive grasping.

The variability in the shapes and sizes of objects presents a significant challenge for two-finger robotic grippers when it comes to manipulating them. Based on the chemistry of vitrimers (a new class of polymer materials that have dynamic covalent bonds, which allow them to reversibly change their mechanical properties under specific conditions), we present two designs as 3D-printed shape memory polymer-based shape-adaptive fingertips (SMP-SAF). The fingertips have two main properties needed for an effective grasping. First, the ability to adapt their shape to different objects. Second, exhibiting variable rigidity, to lock and retain this new shape without the need for any continuous external triggering system. Our two design strategies are: 1) A curved part, which is suitable for grasping delicate and fragile objects. In this mode and prior to gripping, the SMP-SAFs are straightened by the force of the parallel gripper and are adapted to the object by shape memory activation. 2) A straight part that takes on the form of the objects by contact force with them. This mode is better suited for gripping hard bodies and provides a more straightforward shape programming process. The SMP-SAFs can be programmed by heating them up above glass transition temperature (54°C) via Joule-effect of the integrated electrically conductive wire or by using a heat gun, followed by reshaping by the external forces (without human intervention), and subsequently fixing the new shape upon cooling. As the shape programming process is time-consuming, this technique suits adaptive sorting lines where the variety of objects is not changed from grasp to grasp, but from batch to batch.

Introduction of Photolatent Bases for Locally Controlling Dynamic Exchange Reactions in Thermo-Activated Vitrimers.

Vitrimers exhibit a covalently crosslinked network structure, as is characteristic of classic thermosetting polymers. However, they are capable of rearranging their network topology by thermo-activated associative exchange reactions when the topology freezing transition temperature (Tv ) is exceeded. Despite the vast number of developed vitrimers, there is a serious lack of methods that enable a (spatially) controlled onset of these rearrangement reactions above Tv . Herein, we highlight the localized release of the efficient transesterification catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) by the UV-induced cleavage of a photolatent base within a covalently crosslinked thiol-epoxy network. Demonstrated with stress relaxation measurements conducted well above the network's Tv , only the controlled release of TBD facilitates the immediate onset of transesterification in terms of a viscoelastic flow. Moreover, the spatially resolved UV-mediated photoactivation of vitrimeric properties is confirmed by permanent shape changes induced locally in the material.

Photopatternable and Rewritable Epoxy-Anhydride Vitrimers.

The present work highlights a new approach to write, erase, and rewrite micropatterns into the same region of covalent adaptable polymer networks. Thermal curing of an epoxy-terminated o-nitrobenzyl ester (o-NBE) derivative with hexahydrophthalic anhydride in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields a dynamic covalent network, whose solubility is locally controlled by irradiation with ultraviolet (UV) light. The photolysis of the o-NBE chromophores enables a well-defined cleavage of the epoxy-anhydride network, and the formation of soluble photolysis products is confirmed by sol-gel analysis. The photo-induced change in solubility is exploited to inscribe micropatterns by photolithographic techniques and after development in an organic solvent positive tone structures with a feature size of 20 µm are obtained. Due to the thermo-activated exchange reactions of the hydroxyl ester links and the related macroscopic reflow, the polymer patterns are fully erased at temperatures well above the topological freezing transition of the vitrimer network. The regenerated film has a smooth surface topology and can be reused to inscribe new micropatterns via mask lithography.

The Impact of Vitrimers on the Industry of the Future: Chemistry, Properties and Sustainable Forward-Looking Applications.

Thermosets are known to be very reliable polymeric materials for high-performance and light-weight applications, due to their retained dimensional stability, chemical inertia and rigidity over a broad range of temperatures. However, once fully cured, they cannot be easily reshaped or reprocessed, thus leaving still unsolved the issues of recycling and the lack of technological flexibility. Vitrimers, introduced by Leibler et al. in 2011, are a valiant step in the direction of bridging the chasm between thermoplastics and thermosets. Owing to their dynamic covalent networks, they can retain mechanical stability and solvent resistance, but can also flow on demand upon heating. More generally, the family of Covalent Adaptable Networks (CANs) is gleaming with astounding potential, thanks to the huge variety of chemistries that may enable bond exchange. Arising from this signature feature, intriguing properties such as self-healing, recyclability and weldability may expand the horizons for thermosets in terms of improved life-span, sustainability and overall enhanced functionality and versatility. In this review, we present a comprehensive overview of the most promising studies featuring CANs and vitrimers specifically, with particular regard for their industrial applications. Investigations into composites and sustainable vitrimers from epoxy-based and elastomeric networks are covered in detail.