Fast Living 3D Printing via Free Radical Promoted Cationic RAFT Polymerization

The application of reversible deactivation radical polymerization techniques in 3D printing is emerging as a powerful method to build “living” polymer networks, which can be easily postmodified with various functionalities. However, the building speed of these systems is still limited compared to commercial systems. Herein, a digital light processing (DLP)‐based 3D printing system via photoinduced free radical‐promoted cationic reversible addition‐fragmentation chain transfer polymerization of vinyl ethers, which can build “living” objects by a commercial DLP 3D printer at a relatively fast building speed (12.99 cm h−1), is reported. The polymerization behavior and printing conditions are studied in detail. The livingness of the printed objects is demonstrated by spatially controlled postmodification with a fluorescent monomer. Photoinduced 3D printing via free radical‐promoted cationic reversible addition fragmentation chain transfer (RAFT) polymerization is demonstrated in this paper. “Living” objects can be achieved with the ability of postmodification owing to the existence of the RAFT terminals at a fast building speed (12.99 cm h−1).