The chemical functionalization of polyolefins to access responsive materials is a long-standing challenge in materials science. Current protocols do not typically tolerate polar functional groups, and postpolymerization modification often leads to material defects. Here the catalytic synthesis of amine-functionalized polyolefins has been achieved using a two-step catalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP). Furthermore, reduction was used to obtain an aminated polyethylene analogue. This preparation transforms simple starting materials into polar-functionalized polymers with complete atom economy. Utilizing dynamic associative interactions, including hydrogen bonding, these materials demonstrate tunable rheological properties, autonomous self-healing, and unexpected adhesion to polytetrafluoroethylene (PTFE).

Ring-opening metathesis polymerization (ROMP) of two different types of amine-functionalized monomers, aminonorbornenes (ANs) and aminocyclooctenes (ACs), has been studied using [(H2IMes)­(PCy3)­(Cl)2Ru = CHPh] Grubbs second generation catalyst, G2, and [(H2IMes)­(pyr)2(Cl)2Ru = CHPh] Grubbs third generation catalyst, G3. Despite the known detrimental effects of unprotected amine functionalities on Ru-based ROMP catalysts, aminopolyolefins can be readily prepared using G2 and G3. The influence of the amine substituent of the monomer on the polymerization process, as probed by monitoring reaction kinetics, confirmed that the basicity/nucleophilicity of the amine group has a detrimental influence on the ROMP process. Reaction kinetics of homopolymerization of both these classes of monomers revealed faster polymerization of ACs than the more strained AN counterpart, which has been attributed to the favored chelated catalyst resting states in the case of ANs. Hammett studies show increased polymerization rates in the presence of electron-withdrawing aryl amine-containing monomers. These observed kinetic effects were used to advantage in the copolymerization of AN and AC monomers to access a gradient polymer. Polymerization kinetics of combined monomers displayed different reactivity profiles than observed during homopolymerization. Polyolefins with unprotected secondary alkyl amines could be synthesized by leveraging the unfavorable chelate formation in the case of AC monomers. The strategic selection of cyclic alkene and relative positioning of amine substituent allows for the diverse incorporation of secondary amines into polymers by ROMP.

Conductive self-assembled monolayers of host–guest vanadium–oxo cages functionalised with phthalocyaninato YbIII moieties have been formed on gold surfaces.