High‐Density Polyethylene with In‐Chain Photolyzable and Hydrolyzable Groups Enabling Recycling and Degradation

Polyethylenes endowed with low densities of in‐chain hydrolyzable and photocleavable groups can improve their circularity and potentially reduce their environmental persistency. We show with model polymers derived from acyclic diene metathesis polymerization that the simultaneous presence of both groups has no adverse effect on the polyethylene crystal structure and thermal properties. Post‐polymerization Baeyer–Villiger oxidation of keto‐polyethylenes from non‐alternating catalytic ethylene‐CO chain growth copolymerization yield high molecular weight in‐chain keto‐ester polyethylenes ( M n ≈50.000 g mol −1 ). Oxidation can proceed without chain scission and consequently the desirable materials properties of HDPE are retained. At the same time we demonstrate the suitability of the in‐chain ester groups for chemical recycling by methanolysis, and show that photolytic degradation by extended exposure to simulated sunlight occurs via the keto groups.