Hydroaminoalkylation for Amine Functionalization of Vinyl‐Terminated Polyethylene Enables Direct Access to Responsive Functional Materials

While functionalized polyethylenes (PEs) exhibit valuable characteristics, the constraints of existing synthetic approaches limit the variety of readily incorporated functionality. New methods to generate functionalized PEs are required to afford new applications of this common material. We report 100 % atom economic tantalum‐catalyzed hydroaminoalkylation of vinyl‐terminated polyethylene (VTPE) as a method to produce amine‐terminated PE. VTPEs with molecular weights between 2200–16800 g/mol are successfully aminated using solvent‐free conditions. Our catalytic system is efficient for the installation of both aromatic and aliphatic amines, and can be carried out on multigram scale. The associating amine functional groups afford modified material properties, as measured by water contact angle, differential scanning calorimetry (DSC) and polymer rheology. The basic amine functionality offers the opportunity to convert inert PE into stimuli‐responsive materials, such that the protonation of aminated PE affords the generation of functional antibacterial PE films. This paper presents a novel method for producing functionalized polyethylenes (PEs) via a 100 % atom economic tantalum‐catalyzed hydroaminoalkylation of vinyl‐terminated polyethylene (VTPE). Our approach addresses current synthetic challenges by enabling the efficient incorporation of amine functionalities into crystalline PEs in the melt phase. These functional materials have diverse potential applications and here we show that aminated PEs exhibit enhanced material properties, and pH responsive properties results in antibacterial PE films.