Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si-O Bonds.

Abstract

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR2(OR'2)) could expand the functional scope of PE mimics as they possess strong Si-O bonds, excellent oxidative stabilities, and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties while maintaining the high thermal stability of HDPE. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si-O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si-O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.