Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates.

Partly or fully renewable (co)polymers are gaining interest in both academia and industry. Polyethylene is a widely used polymer, classically derived from fossil fuels, with a high versatility stemming from the introduction of comonomers altering the mechanical properties. The introduction of renewable functionalities into this polymer is highly attractive to obtain functional, tunable, and at least partially renewable polyethylenes. We herein report the introduction of biosourced cyclic carbonates into polyethylene using organometallic-mediated radical polymerization under mild conditions. Molecular weights of up to 14 600 g mol -1 with dispersities as low as 1.19 were obtained, and the cyclic carbonate content could be easily tuned by the ethylene pressure during the polymerization. As a proof of concept, the hydrolysis of the cyclic carbonates of a representative copolymer was explored, and it provided polyethylene-bearing vicinal diols, with a hydrolysis degree of 71%. Given the multitude of chemoselective modifications possible on cyclic carbonates as well as the fact that many allylic- and alkylidene-type cyclic carbonates are accessible from renewable resources, this work opens up an avenue for the design of functional and more sustainable polyethylenes.