Kinetics, mechanisms, and synthesis studies of ring‐opening‐closing alternating copolymerization

Abstract

AbstractThe present paper describes the ring‐opening‐closing alternating copolymerization of cyclic phosphonites (2‐phenyl‐1,3,2‐dioxaphosphelane (1a), 2‐phenyl‐1,3,2‐dioxaphosphorinane(1b), 2‐phenyl‐1,3,2‐dioxaphosphepane(1c), and 2‐phenyl‐4H‐1,3,2‐benzodioxa phosphorin‐4‐one(1d)) with muconic acid(2a), succinaldehyde(2b), glutaraldehyde(2c), adipinaldehyde(2d), o‐phthalaldehyde(2e), acrylic anhydride(2f), methacrylic anhydride(2g), N‐methyl diacrylamide(2h), and N‐methyldimethacrylamide(2i). The reaction of a 1:1 monomer feed ratio, explained by a mechanism of propagation via zwitterion intermediates, proceeds without any added catalyst to give an alternating copolymer 3 involving ring‐opening of 1 and ring‐closing of 2. The structure of copolymer 3 was determined by1 H,13 C NMR,31 P NMR and IR spectroscopies as well as elemental analysis.