Abstract
Atom transfer radical polymerization (ATRP) is one of the most robust tools to prepare well-defined polymers with precise topologies and architectures. Although series of improved ATRP methods have been developed to decrease the metal catalyst loading to parts per million, metal residue is the key limiting factor for variety of applications, especially in microelectronic and biomedical area. The feasible solution to this challenge would be the establishment of metal-free ATRP. Since 2014, organocatalyzed ATRP (O-ATRP) or metal free ATRP has achieved significant progress by developing kinds of organic photoredox catalysts. This review highlights the advances in organocatalyzed atom transfer radical polymerization as well as the potential future directions.
Highlights
Reversible deactivation radical polymerization (RDRP) (controlled radial polymerization (CRP)) has achieved signi cant progress in precision polymer synthesis, which includes but not limited to atom transfer radical polymerization (ATRP) [1,2,3,4], reversible addition–fragmentation polymerization (RAFT) [5, 6] and nitroxide-mediated polymerization (NMP) [7], etc
For the classical ATRP system, alkyl halide initiator was quickly activated by low valence state copper (Cu(I)) to form the propagating radical and the oxidation state metal (Cu(II)) [1,2,3,4]. e radicals were deactivated by the deactivating species (Cu(II)) to yield dormant species. e excellent control over the polymerization process relies on this activation/ deactivation equilibrium. e principles of organocatalyzed atom transfer radical polymerization are the development of novel organic photoredox catalysts, which could maintain the activation/deactivation equilibrium
It was found that keeping the phenoxazine catalyst with planar conformation during the catalytic cycle would facilitate the preparation of well-de ned polymers. With these rules in mind, a substituted phenoxazine (3,7-di(4-biphenyl) 1-naphthalene-10-phenoxazine) was explored as a visible light photoredox catalyst that indicated better performance comparing with UV-absorbing phenoxazines and other photoredox catalyst in organocatalyzed ATRP (O-ATRP)
Summary
Reversible deactivation radical polymerization (RDRP) (controlled radial polymerization (CRP)) has achieved signi cant progress in precision polymer synthesis, which includes but not limited to atom transfer radical polymerization (ATRP) [1,2,3,4], reversible addition–fragmentation polymerization (RAFT) [5, 6] and nitroxide-mediated polymerization (NMP) [7], etc. Metal free ATRP or organocatalyzed ATRP (O-ATRP) has been established based on series of organic photoredox catalysts with various polymerization mechanisms [32,33,34,35]. It provides a viable and ideal solution for addressing the challenge of metal catalyst residue contamination. It provides a viable and ideal solution for addressing the challenge of metal catalyst residue contamination. is Advances in Polymer Technology review focuses on the advances in organocatalyzed atom transfer radical polymerization as well as the potential future directions
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