Mechanochemical Backbone Editing for Controlled Degradation of Vinyl Polymers

• Published in: Angewandte Chemie International Edition 2024-08, Vol.63 (33), p.e202408225-n/a
• Main Authors: Li, Zhuang, Zhang, Xiaohui, Zhao, Yajun, Tang, Shan
• Format: Article
• Language: English
• Subjects: backbone editing; Ball milling; Chains (polymeric); Comminution; Copolymerization; Degradation; Editing; Environmental degradation; polyacrylates; polymer degradation; polymer mechanochemistry; Polymers; RAFT polymerization; Saturated hydrocarbons; Succinimide; Vinyl polymers
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202408225

The chemically inert nature of fully saturated hydrocarbon backbones endows vinyl polymers with desirable durability, but it also leads to their significant environmental persistence. Enhancing the sustainability of these materials requires a pivotal yet challenging shift: transforming the inert backbone into one that is degradable. Here, we present a versatile platform for mechanochemically editing the fully saturated backbone of vinyl polymers towards degradable polymer chains by integrating cyclobutene‐fused succinimide (CBS) units along backbone through photo‐iniferter reversible addition‐fragmentation chain‐transfer (RAFT) copolymerization. Significantly, the evenly insertion of CBS units does not compromise thermal or chemical stability but rather offers a means to adjust the properties of polymethylacrylate (PMA). Meanwhile, reactive acyclic imide units can be selectively introduced to the backbone through mechanochemical activation (pulse ultrasonication or ball‐milling grinding) when required. Subsequent hydrolysis of the acyclic imide groups enables efficient degradation, yielding telechelic oligomers. This approach holds promise for inspiring the design and modification of more environmentally friendly vinyl polymers through backbone editing. The hydrocarbon backbone of vinyl polymers can be edited by mechanical force to achieve controlled degradation, wherein the cyclobutene‐fused succinimide comonomer can be incorporated into the backbone of vinyl polymers through a photo‐iniferter RAFT copolymerization pathway. The key aspect is that the cyclobutane units preserve the integrity of the polymer backbone during material application, while the cleavable imide groups can be selectively exposed through backbone editing upon mechanochemical activation. Subsequent hydrolysis of the imides facilitates efficient degradation and upcycling, resulting in the production of telechelic oligomers. This research holds the potential to inspire the design and modification of vinyl polymers through backbone editing.