The impact of dynamic bonding associations on the rheology of amine containing polyolefins

Polyolefins are utilized in a wide array of applications due to their desirable and predictable properties. The incorporation of polar functional groups into the nonpolar backbone imparts an opportunity to further tune the properties and broaden the application space. Among the library of H-bonding chemistries that have been implemented via post-polymerization modifications, amines are of particular interest due to their challenging syntheses. The discovery of a two-step catalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP) has opened access to a new class of amine containing polyolefins, transforming simple starting materials into polar-functionalized polymers with complete atom economy. New rheological properties emerge due to the dynamic associative interactions, including H-bonding, [Formula: see text] stacking, and aggregate clustering, which are highly tunable based on the molecular design. The amine containing polyolefins also demonstrate autonomous self-healing and adhesion to low surface energy substrates, with particular interest in advanced adhesive systems. This review article details the recent progress in the molecular design of amine containing polyolefins, and the diversity of linear, non-linear, and extensional rheological behaviors. A discussion into remaining challenges in our understanding of the complex microstructure of the amine containing polyolefins and future pathways to designer materials from simple starting feedstocks is also presented.