Dynamically cross-linkable bottlebrush polymer adhesives were synthesized by the grafting-from strategy through a combination of ring-opening metathesis polymerization (ROMP) and photoiniferter polymerization. A norbornene-containing trithiocarbonate was first polymerized by ROMP to form the bottlebrush polymer backbone; this was followed by blue-light-mediated photoiniferter polymerization of butyl acrylate initiated by the poly(trithiocarbonate) to form the bottlebrush polymer. This strategy afforded well-defined bottlebrush polymers with molar masses in excess of 11 000 kg/mol. For un-cross-linked bottlebrush polymers, 180° peel tests revealed a cohesive failure mode and showed similar peel strengths (∼30 g/mm) regardless of the backbone polymer degree of polymerization (DP). The bottlebrush polymers were then treated with butylamine to remove the trithiocarbonate, liberating thiols on each side-chain terminus. In the presence of oxygen, these thiols readily cross-linked via disulfide bond formation. The cross-linked bottlebrush polymers with a backbone DP of 400 showed a greater than sixfold improvement in peel strength, whereas those with a backbone DP of 100 exhibited a twofold enhancement compared with un-cross-linked samples along with a change to adhesive failure. Triphenylphosphine readily reduced the disulfide bonds, effectively removing all cross-links in the bottlebrush network and allowing for recasting of the adhesive, which showed similar adhesive and rheological properties to the original un-cross-linked samples.

Ureido-cytosine pendant groups contributed to random acrylic copolymers with enhanced thermomechanical performance, well-defined morphologies, and reduced water uptake.

Styrenic DABCO salt monomers enabled synthesis of microphase-separated ionomers with doubly-charged pendant groups.

This manuscript describes the structure–property–morphology relationships of doubly charged 1,4-diazabicyclo[2.2.2]­octane (DABCO) salt-containing ABA triblock ionomers. The triblock copolymers consist a soft poly­(n-butyl acrylate) (PnBA) central block and two external styrenic hard blocks bearing amphiphilic pendant C18-alkyl groups and doubly charged salt units. Surprisingly, the DABCO salt-containing ABA block copolymers preserved the thermomechanical integrity until degradation, which indicated the formation of a reinforcing physical network compared to the corresponding doubly charged random copolymers and singly charged block copolymer analogs. Small-angle X-ray scattering data revealed that the DABCO-based ABA block copolymers self-assembled into highly ordered hierarchical microstructures, in which the soft and hard domain of the block copolymers phase-separated into highly ordered lamellar morphologies. Moreover, a secondary structure that originated from the ordering of the amphiphilic pendant groups formed within the lamellar hard domain. The interesting thermal, thermomechanical, and morphological properties of doubly charged ionic block copolymers open promising avenues for the synthesis of novel thermoplastic elastomers.