Cobalt-Catalysed Chain Transfer Polymerisation Enables Soft Methacrylate Nematic Elastomers for Switchable Pressure-Sensitive Adhesion

Abstract

Liquid crystal elastomers (LCEs) exhibit unique viscoelastic behavior arising from reversible liquid-crystalline ordering, making them attractive candidates for switchable pressure-sensitive adhesives (PSAs). However, methacrylate-based LCEs are typically highly crosslinked, leading to elevated glass-transition temperatures ($T_g$) and storage moduli ($E'$) that limit adhesive performance. Here, we demonstrate that catalytic chain-transfer polymerization provides an effective strategy for engineering soft methacrylate nematic elastomers through systematic control of network architecture. Incorporation of parts-per-million concentrations of bis(boron difluorodimethylglyoximate)cobalt(II) (CoBF) during photopolymerization reduced the effective crosslink density and increased the molecular weight between crosslinks, producing substantial decreases in $T_g$ and $E'$ while preserving nematic order. Dynamic mechanical analysis revealed that increasing CoBF concentration enhanced viscoelastic dissipation and broadened the accessible nematic temperature window. To further optimize rheological properties for pressure-sensitive adhesion, monofunctional methacrylates and flexible poly(ethylene glycol) dimethacrylate (PEGDMA) were incorporated into the network. The optimized formulation exhibited a $T_g$ near 0~$^\circ$C, a room-temperature storage modulus of approximately 0.3 MPa, and high damping behavior, approaching the Dahlquist criterion for pressure-sensitive adhesion. As a result, the resulting nematic elastomers displayed strong tack, peel, and lap-shear adhesion in the nematic state, together with rapid, reversible, and residue-free debonding upon heating above the nematic-to-isotropic transition temperature.