Liquid Crystalline Vitrimers with Full or Partial Boronic‐Ester Bond Exchange

Abstract In this manuscript, a new vitrimer chemistry strategy (boronic transesterification) is introduced into liquid crystal elastomers (LCEs) to allow catalyst‐free bond exchange to enable processing (director alignment, remolding, and welding) in the liquid crystalline (nematic) phase. Additionally, the concept of partial vitrimer network is explored, where a percolating fraction of the network remains permanently cross‐linked, hence preserving the integrity of the materials and preventing large creep. This combined strategy allows one to avoid the shortcomings of current methods of aligning LCE, especially in complex shapes. Thiol‐acrylate Michael addition reaction is used to produce uniform polymer networks with controllable thermomechanical response and local plasticity. Control of the plasticity is achieved by varying the fractions of permanent and exchangeable network, where a material “sweet spot” with an optimum elastic/plastic balance is identified. Such exchangeable LCE (xLCE) allows postpolymerization processing, while also minimizing unwanted creep during actuation. Moreover, conjoining multiple materials (isotropic and liquid‐crystalline) in a single covalently bonded composite structure results in a variety of smart morphing systems that adopt shapes with complex curvature. Remolding and welding xLCEs may enable the applications of these materials as mechanical actuators in reversibly folding origami, in vivo artificial muscles, and in soft robotics.