Design of an Ultrafast and Controlled Visible Light‐Mediated Photoiniferter RAFT Polymerization for Polymerization‐Induced Self‐Assembly (PISA)
Zilong Wu, Zhengyan He, Yuchen Zhou, Tongtong Kou, Kaili Gong, Fuchun Nan, Terefe Tafese Bezuneh, Shiguo Han, Cyrille Boyer, William W. Yu
Abstract
In this contribution, we designed a new xanthate RAFT agent by introducing (5,6,7,8-tetrahydro-2-naphthalenyl)oxy (TNO) as the Z group, namely 2-[(((5,6,7,8-Tetrahydro-2-naphthalenyl)oxycarbonothioyl)thio)ethyl propanoate] (TNXEP). Due to the presence of the TNO group, TNXEP enabled highly controlled and ultrafast photoiniferter RAFT polymerization under violet (λ=405 nm) and blue (λ=450 nm) light. This approach was effectively extended to aqueous media for polymerization-induced self-assembly (PISA), facilitating the synthesis of polymeric nanoparticles. Leveraging the rapid photolysis and extended absorption of TNXEP, we demonstrated the first photoiniferter PISA system realizing ultrafast polymerization (>90 % monomer conversion in minutes) under visible light irradiation. Enhanced visible light penetration improved photopolymerization uniformity, enabling rapid and scalable production of polymeric nanoparticles at a 30 g scale in just 10 minutes, with tunable morphologies, including spheres, worms, and vesicles.