An Expedient Route to Bio‐based Polyacrylate Alternatives with Inherent Degradation Capabilities by Organic Catalysis for Polymerization of Muconate Esters

Abstract 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]‐2 5,4 5 catenadi(phosphazene) (P 4 ‐ 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.