Poly(cyclic vinyl ethers) (PCVEs), compositions of same, methods of making same, and uses of same. In various examples, PCVEs (e.g., homopolymers and / or copolymers) comprise repeat units comprising cyclic
vinyl ether (CVE) groups in the backbone (e.g., poly(2,3-dihydrofuran) and / or poly(3,4-
dihydropyran)). In various examples, PCVE homopolymers comprise molecular weights (Mn and / or Mw) of 200
kilodalton (kD) or greater. In various examples, PCVE copolymers (e.g., random or block) comprise one or more CVE group(s) and / or additional (e.g., acyclic
vinyl ether (AVE) and / or styrenic) group(s)). A method of preparing PCVEs comprises polymerizing monomers comprising CVE groups (e.g., 2,3-dihydrofuran and / or 3,4-
dihydropyran). In various examples, pentakis(carbonylcyclopentadienes) (PCCPs) and / or
hydrogen bond donors are
polymerization catalysts and / or initiators. various examples, PCVEs are biorenewable, recyclable,
thermoplastic materials that exhibit desirable optical
clarity, desirable barrier properties to, e.g.,
oxygen,
carbon dioxide, and water, and find uses in
food packaging, windows, and the like.