Abstract:
Amine-functionalized polyolefins are an underdeveloped class of functional materials useful for their self-healing, adhesive, antimicrobial, and carbon capture properties. The nucleophilicity, basicity, and polarity imparted by amines allow for further synthetic elaboration or responsive material applications, making this class of polyolefins highly desirable. Their troublesome synthesis is a result from polymerization catalyst inhibition by the amine; or uncontrolled radical reactivity in postpolymerization modification methods which results in poor polymer microstructure. Here, it is shown that postpolymerization hydroaminoalkylation is a promising, green, alternative to current amine-functionalized polymer syntheses. This catalytic reaction is 100% atom economic, installing unprotected amines onto alkene containing polyolefins. Hydroaminoalkylation is broadly applicable, coupling a variety of aryl and alkyl amine substrates with the polyolefin in a single step. Further, hydroaminoalkylation is catalyzed by early transition metals, which are more abundant and less toxic than late transition metals, and the reactions can be performed in solvent-free conditions. This work overcomes current limitations in amine-functionalized material synthesis by offering an inexpensive and rapid method to produce a new class of amine containing polymers. In this presentation, current advances on tuning amine incorporation and accessible polymeric alkene substrates will be presented, along with implications of the amine functionality on material properties.