Exchangeable Liquid Crystalline Elastomers and Their Applications.

This Review presents and discusses the current state of the art in "exchangeable liquid crystalline elastomers", that is, LCE materials utilizing dynamically cross-linked networks capable of reprocessing, reprogramming, and recycling. The focus here is on the chemistry and the specific reaction mechanisms that enable the dynamic bond exchange, of which there is a variety. We compare and contrast these different chemical mechanisms and the key properties of their resulting elastomers. In the conclusion, we discuss the most promising applications that are enabled by dynamic cross-linking and present a summary table: a library of currently available materials and their main characteristics.

Rates of transesterification in epoxy-thiol vitrimers.

Vitrimers, an important subset of dynamically crosslinked polymer networks, have many technological applications for their excellent properties, and the ability to be re-processed through plastic flow above the so-called vitrification temperature. We report a simple and efficient method of generating such adaptive crosslinked networks relying on transesterification for their bond exchange by utilising the 'click' chemistry of epoxy and thiols, which also has the advantage of a low glass transition temperature. We vary the chemical structure of thiol spacers to probe the effects of concentration and the local environment of ester groups on the macroscopic elastic-plastic transition. The thermal activation energy of transesterification bond exchange is determined for each chemical structure, and for a varying concentration of catalyst, establishing the conditions for the optimal, and for the suppressed bond exchange. However, we also discover that the temperature of elastic-plastic transition is strongly affected by the stiffness (dynamic rubber modulus) of the network, with softer networks having a much lower vitrification temperature even when their bond-exchange activation energy is higher. This combination of chemical and physical control factors should help optimise the processability of vitrimer plastics.

Imine-Based Reactive Mesogen and Its Corresponding Exchangeable Liquid Crystal Elastomer.

To date, exchangeable liquid crystalline elastomers (xLCEs) have been mainly fabricated by combining conventional LCEs with additional exchangeable functional groups in their networks. While conventional LCEs are frequently made from commercially available aromatic-ester reacting mesogens or from mesogens based on a biphenyl core, such reacting monomers are not optimized to fabricating xLCEs whose bond-exchange reaction is fast and clean cut. Here, we develop a fast synthesis route to produce a new type of reactive mesogen based on an aromatic-imine structure that intrinsically enables a fast and stable bond-exchange reaction in the resulting imine-based xLCE. This new xLCE displays vitrimer plastic-flow behavior, and its bond-exchange activation energy is calculated to be 54 kJ/mol. We also demonstrate that this xLCE is thermally stable to withstand many recycling cycles without visible decay, and its liquid crystallinity is preserved. Finally, we demonstrate the reprogramming and realignment of the mesogen orientation in this xLCE with the realigned xLCE capable of reversible thermal actuation.