Creation of strong and tough plastics from sustainable and biorenewable resources is a significant challenge in polymer science. This challenge is further complicated when attempting to make these materials using an economically viable process, which is often hindered by the production and availability of chemical feedstocks and the efficiency of the monomer synthesis. Herein, we report the synthesis and characterization of a strong thermoplastic made from 2,3-dihydrofuran (DHF), a monomer made in one step from 1,4-butanediol, a bioalcohol already produced on the plant scale. We developed a green, metal-free cationic polymerization to enable the production of poly(2,3-dihydrofuran) (PDHF) with molecular weights of up to 256 kg/mol at room temperature. Characterization of these polymers showed that PDHF possesses high tensile strength and toughness (70 and 14 MPa, respectively) comparable to commercial polycarbonate, high optical clarity, and good barrier properties to oxygen, carbon dioxide, and water. These properties make this material amenable to a variety of applications, from food packaging to high strength windows. Importantly, we have also developed a facile oxidative degradation process of PDHF, providing an end-oflife solution for PDHF materials.

Cationic polymerization enables production of sustainable thermoplastic elastomers constructed from renewable vinyl ethers and -p-methoxystyrene with properties consistent with their petroleum-derived counterparts.

Cationic polymerizations of vinyl ethers have gained recent attention due to their ability to produce robust, biorenewable materials. These developments have been largely enabled by the advent of cationic reversible addition−fragmentation chain-transfer (RAFT) polymerization; however, the scalability and sustainability of this method are hindered by current chain-transfer agents (CTAs), which exist as viscous, colored oils requiring complex syntheses and solvent-intensive purification. Herein, we produce a solid, colorless CTA through a green synthetic route in 83% yield on a 50-gram scale. We investigate the utility of this CTA in chemical, electrochemical, photochemical, and acid-initiated methods, revealing that it achieves efficient polymerization with excellent control over molecular weight, low dispersity values, high chain end fidelity, and temporal control in cationic RAFT polymerizations.