Reactive Compression Molding Post-Inverse Vulcanization: A Method to Assemble, Recycle, and Repurpose Sulfur Polymers and Composites

Graphical Abstract

Under pressure: The reactive interfaces of rubber polysulfides made by inverse vulcanization bond together when heated with compression. The S−S metathesis reaction occurs at relatively low temperature and allows additive assembly, recycling, and repurposing of these materials, as well as the preparation of composites.

Abstract

Inverse vulcanization provides dynamic and responsive materials made from elemental sulfur and unsaturated cross-linkers. These polymers have been used in a variety of applications such as energy storage, infrared optics, repairable materials, environmental remediation, and precision fertilizers. In spite of these advances, there is a need for methods to recycle and reprocess these polymers. In this study, polymers prepared by inverse vulcanization are shown to undergo reactive compression molding. In this process, the reactive interfaces of sulfur polymers are brought into contact by mechanical compression. Upon heating these molds at relatively low temperatures (≈100 °C), chemical bonding occurs at the polymer interfaces by S−S metathesis. This method of processing is distinct from previous studies on inverse vulcanization because the polymers examined in this study do not form a liquid phase when heated. Neither compression nor heating alone was sufficient to mold these polymers into new architectures, so this is a new concept in the manipulation of sulfur polymers. Additionally, high-level ab initio calculations revealed that the weakest S−S bond in organic polysulfides decreases linearly in strength from a sulfur rank of 2 to 4, but then remains constant at about 100 kJ mol⁻¹ for higher sulfur rank. This is critical information in engineering these polymers for S−S metathesis. Guided by this insight, polymer repair, recycling, and repurposing into new composites was demonstrated.