Mechanochemical synthesis of inverse vulcanized polymers

Abstract Inverse vulcanization, a sustainable platform, can transform an industrial by-product, sulfur, into polymers with broad green applications such as heavy metal capture and recyclable materials. However, the process usually requires high temperatures (≥159°C), and the crosslinkers needed to stabilise the sulfur are therefore limited to high-boiling-point monomers only. Here, we report an alternative route for inverse vulcanization — mechanochemical synthesis (MS), with advantages of mild conditions (room temperature), short reaction time (3 h), high atom economy, less H2S, and broader monomer range. Successful generation of polymers using crosslinkers ranging from aromatic, aliphatic to volatile, including renewable monomers, demonstrates this method is powerful and versatile. Compared with thermal synthesis, the MS products show enhanced mercury capture. The resulting polymers show thermal and light induced recycling. The speed, ease, versatility, safety, and green nature of this process offers a more sustainable future for inverse vulcanisation, and enables further unexpected discoveries.