A one‐step synthesis of heterobifunctional hyperbranched polyethylenes covalently tethered with dual acryloyl and 2‐bromoisobutyryl functionalities at controllable contents is reported. It is achieved in one pot by chain‐walking terpolymerization of ethylene with two functional acrylate comonomers, 1,6‐hexanediol diacrylate and 2‐(2‐bromoisobutyryloxy) ethyl acrylate. The unique chain‐walking mechanism renders the hyperbranched polymer chain topology and its remarkable capability in incorporating acrylate comonomers enables the incorporation of both comonomers to give two valuable functionalities. The two comonomers exhibit nearly equal vinyl reactivity and are incorporated independently in the terpolymerization with their molar contents controlled by adjusting the comonomer feed concentrations. magnified image

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