Degradable thermosets via orthogonal polymerizations of a single monomer

• 成果类型: Article
• 署名作者: Dreiling, Reagan J.; Huynh, Kathleen; Fors, Brett P.
• 署名单位: Cornell University
• 刊物名称: Nature
• ISSN/ISSBN: 0028-1005
• DOI: 10.1038/s41586-024-08386-w
• 发表日期: 2025-02-01
• 页码: 120-+
• 关键词: bifunctional monomer; copolymerization; catalysts; polymers; atrp

摘要

Crosslinked thermosets are highly durable materials, but overcoming their petrochemical origins and inability to be recycled poses a grand challenge(1, 2-3). Many strategies to access crosslinked polymers that are bioderived or degradable-by-design have been proposed, but they require several resource-intensive synthesis and purification steps and are not yet feasible alternatives to conventional consumer materials(4, 5, 6, 7-8). Here we present a modular, one-pot synthesis of degradable thermosets from the commercially available, biosourced monomer 2,3-dihydrofuran (DHF)(9). In the presence of a ruthenium catalyst and photoacid generator, DHF undergoes slow ring-opening metathesis polymerization to give a soft polymer; then, exposure to light triggers strong acid generation and promotes the cationic polymerization of the same DHF monomer to spatially crosslink and strengthen the material(10, 11-12). By manipulating catalyst loading and light exposure, we can access materials with physical properties spanning orders of magnitude and achieve spatially resolved material domains. Importantly, the DHF-based thermosets undergo stimuli-selective degradation and can be recycled to the monomer under mild heating. The use of two distinct polymerization mechanisms on a single functional group allows the synthesis of degradable and recyclable thermoset materials with precisely controlled properties.