The quest for polymers that would be at the same time bio‐based and degradable after usage, in addition to offering chemical post‐modification options, remains a daunting challenge in contemporary polymer science. Despite advances in polymer chemistry, attempts at controlling the chain‐growth polymerization of muconate esters remain unexplored. Here we show that dialkyl muconates can be rapidly polymerized by organocatalyzed group transfer polymerization (O‐GTP). O‐GTP is conducted to completion at room temperature in toluene within a few minutes, using 1‐ethoxy‐1‐(trimethylsiloxy)‐1,3‐butadiene (ETSB) as initiator and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)‐phosphoranylidenamino]‐25,45 catenadi(phosphazene) (P4‐t­‐Bu) as catalyst. Chain extension experiments and synthesis of all muconate‐type block copolymers can also be achieved. Furthermore, polymuconates are amenable to facile post‐polymerization modification reactions. This is showcased through the hydrolysis of the ester side chains leading to well‐defined poly(muconic acid), and by epoxidation of the C=C double bonds of the main chain. Last but not least, these internal alkene groups can be selectively cleaved by ozonolysis, demonstrating the upcyclability of polymuconates under oxidative conditions. This work demonstrates that polymuconates constitute a unique platform of bio‐based polymers, easily modifiable in addition to being chemically degradable under user friendly experimental conditions.

中文翻译：

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通过有机催化粘康酸酯聚合获得具有固有降解能力的生物基聚丙烯酸酯替代品的便捷途径


除了提供化学后改性选项之外，寻求同时具有生物基和使用后可降解的聚合物仍然是当代聚合物科学中的一项艰巨挑战。尽管聚合物化学取得了进步，但控制粘康酸酯链增长聚合的尝试仍未得到探索。在这里，我们证明粘康酸二烷基酯可以通过有机催化基团转移聚合（O-GTP）快速聚合。使用 1-乙氧基-1-(三甲基硅氧基)-1,3-丁二烯 (ETSB) 作为引发剂和 1-叔丁基-4,4,4，O-GTP 在室温下在甲苯中几分钟内完成-三(二甲氨基)-2,2-双[三(二甲氨基)-正膦基氨基]-25,45 链二(磷腈) (P4-t-Bu) 作为催化剂。还可以实现所有粘康酸酯型嵌段共聚物的扩链实验和合成。此外，聚粘康酸酯易于进行聚合后改性反应。这通过酯侧链的水解产生明确的聚粘康酸以及主链的 C=C 双键的环氧化来证明。最后但并非最不重要的一点是，这些内部烯烃基团可以通过臭氧分解选择性裂解，证明了聚粘康酸酯在氧化条件下的升级循环能力。这项工作表明，聚粘康酸酯构成了独特的生物基聚合物平台，除了在用户友好的实验条件下可化学降解之外，还易于修饰。