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<p>Vinyl ethers, while being typical monomers for living cationic polymerization, have limited commercial use due to the poor mechanical properties of their polymers at room temperature. We explored the use of photoacid generators to induce cationic reversible addition-fragmentation chain transfer (RAFT) polymerization for the rapid high-resolution three-dimensional (3D) printing of various vinyl ethers. The process demonstrated controlled molecular weights and narrow molecular weight distributions (MWD), with monomer conversions exceeding 90% in minutes. Incorporating a crosslinker enabled 3D printing at speeds up to 8.46 cm h<sup>−1</sup> with layer thicknesses as thin as 50 µm. The mechanical properties of the printed objects were tunable by adjusting resin components, allowing for a range of material characteristics from brittle to elastomeric (tensile strength ranging from 13.9 to 31.7 MPa, Young’s modulus ranging from 185.6 to 992.7 MPa and elongation at break ranging from 2.8% to 68.3%). Moreover, polymer welding facilitated the creation of gradient materials, showcasing the potential for engineered applications of poly(vinyl ethers) (PVEs).</p>

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Rapid and high-resolution 3D printing via photoacid generator induced cationic RAFT polymerization

  • 期刊论文

  • 发表日期：

    2025年1月8日

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  • Bowen Zhao,
  • Jiajia Li,
  • Chongyang Yang,
  • Xiangqiang Pan,
  • Zhengbiao Zhang,
  • Jian Zhu

摘要

Vinyl ethers, while being typical monomers for living cationic polymerization, have limited commercial use due to the poor mechanical properties of their polymers at room temperature. We explored the use of photoacid generators to induce cationic reversible addition-fragmentation chain transfer (RAFT) polymerization for the rapid high-resolution three-dimensional (3D) printing of various vinyl ethers. The process demonstrated controlled molecular weights and narrow molecular weight distributions (MWD), with monomer conversions exceeding 90% in minutes. Incorporating a crosslinker enabled 3D printing at speeds up to 8.46 cm h−1 with layer thicknesses as thin as 50 µm. The mechanical properties of the printed objects were tunable by adjusting resin components, allowing for a range of material characteristics from brittle to elastomeric (tensile strength ranging from 13.9 to 31.7 MPa, Young’s modulus ranging from 185.6 to 992.7 MPa and elongation at break ranging from 2.8% to 68.3%). Moreover, polymer welding facilitated the creation of gradient materials, showcasing the potential for engineered applications of poly(vinyl ethers) (PVEs).