Photo-Mediated RAFT Step-Growth Polymerization With Diacrylate Monomers: Investigating Versatility and Oxygen Tolerance.

Photomediated reversible addition fragmentation chain transfer (RAFT) step-growth polymerization is performed using a trithiocarbonate-based chain transfer agent (CTA) and acrylate-based monomers both with and without a photocatalyst. The versatility of photo-mediated RAFT step-growth is demonstrated by one-pot synthesis of a graft copolymer via sequential monomer addition. Furthermore, oxygen-tolerant photo-mediated RAFT step-growth is demonstrated, facilitated by the appropriate selection of photocatalyst and solvent pair (zinc tetraphenyl porphyrin [ZnTPP] and dimethyl sulfoxide [DMSO]), enabling ultralow volume polymerization under open-air conditions.

RAFT step-growth polymerization the Z-group approach and deconstruction by RAFT interchange.

Recycling vinyl polymers is essential to mitigate the environmental impact of plastic waste. However, typical polymerization strategies to construct vinyl polymers lack the ability to incorporate degradable linkers throughout the main chain. We report a RAFT step-growth polymerization through the Z-group approach that is directly carried out by using a common class of symmetric trithiocarbonate based RAFT agents and commercially available bismaleimide monomers.

Polymer Functionalization by RAFT Interchange.

Here, we report a simple approach for end group functionalization of linear polymers and graft copolymers via an interchange process of reversible addition-fragmentation chain transfer (RAFT) polymerization chain transfer agents (CTAs). The high functional group tolerance of the RAFT process allows a library of functionalities to be introduced. Moreover, this approach allows multiple functional groups to be installed simultaneously.

Step-growth polymerization by the RAFT process.

Reversible Addition-Fragmentation Chain Transfer (RAFT) step-growth polymerization is an emerging method that synergistically combines the benefits of RAFT polymerization (functional group and user-friendly nature) and step-growth polymerization (versatility of the polymer backbone). This new polymerization method is generally achieved by using bifunctional reagents of monomer and Chain Transfer Agent (CTA), that efficiently yield Single Monomer Unit Insertion (SUMI) adducts under stoichiometrically balanced conditions. This review covers a brief history of the RAFT-SUMI process and its transformation into RAFT step-growth polymerization, followed by a comprehensive discussion of various RAFT step-growth systems.