Orthogonal synthesis and modification of hyperbranched polymers via different colors of light

Abstract

A versatile and straightforward approach for the synthesis of functional hyperbranched polymers with tunable properties is represented utilizing a chromatic orthogonal protocol. The method involves the combination of photo‐induced electron/energy transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) and self‐condensing vinyl polymerization (SCVP) under visible light irradiation leading to the formation of hyperbranched polymers with well‐defined properties possessing photo‐caged diene moieties. Upon UV light irradiation, the remaining photoenol functionality was efficiently activated for the post‐functionalization of the synthesized hyperbranched polymers with maleimide functional molecules via Diels‐Alder photo‐click chemistry. Both low molar mass and polymeric maleimide functional click components, namely N‐phenylmaleimide, poly(ethylene glycol)‐maleimide and polycaprolactone‐maleimide were quantitively attached onto the hyperbranched polymers under ambient conditions. The results obtained from our protocol indicate high efficiency and convenience, offering a straightforward strategy for the design and synthesis of functionalized hyperbranched polymers. The chromatic orthogonal nature of the protocol enables precise control over the modification process, adding versatility to the materials obtained. Overall, this research lays the groundwork for novel pathways in material design, opening new possibilities for advanced materials with tailored properties.