Tuning the Mechanical Properties of 3D-printed Objects by Mixing Chain Transfer Agents in Radical Promoted Cationic RAFT Polymerization

The utilization of (cationic) reversible addition-fragmentation chain transfer (RAFT) polymerization in photoinduced three-dimensional (3D) printing has emerged as a robust technique for fabricating a variety of stimuli-responsive materials. However, methods for precisely adjusting the mechanical properties of these materials remain limited, thereby constraining their broader applicability. In this study, a facile way is introduced to modulate the mechanical properties of 3D printed objects by mixing two chain transfer agents (CTAs) within a radical-promoted cationic RAFT (RPC-RAFT) polymerization-based 3D printing process. Through systematic investigations employing tensile testing and dynamic mechanical analysis (DMA), the influence of CTA concentration and molar ratio between two CTAs on the mechanical behavior of the printed objects are explored. These findings demonstrate that higher concentrations of CTAs or a greater molar ratio of the more active CTA within the mixed CTAs result in decreased Young's modulus and glass transition temperatures of the printed objects. Moreover, the tensile failure strain increased with the increasing CTA content, i.e., the samples became more ductile. This methodology broadens the toolbox available for tailoring the mechanical properties of 3D printed materials. A facile method to tune the mechanical properties of 3D-printed polymeric materials is developed. This strategy is realized via polymer dispersity control by manipulating the molar ratio between two chain transfer agents in radical-promoted cationic reversible addition-fragmentation chain transfer (RPC-RAFT) polymerization, which has essential impacts on the homogeneity of polymer network. image