Recycling of Polydicyclopentadiene Enabled with N-Coordinated Boronic Ester Bonds

In this contribution, the transformation of polydicyclopentadiene (PDCPD) from thermoset into vitrimer is introduced. First, two N-coordinated diboronic diols are successfully synthesized via the reaction of N,N,N-tri(2-hydroxyethyl)amine and/or N,N,N",N"-tetrakis(2-hydroxyethyl)ethylene diamine with 4-(hydroxymethyl) phenylboronic acid and then they are transformed into two N-coordinated cyclic boronic diacrylates. The latter two dienes carrying electron-withdrawing substituents are used for the ring opening insertion metathesis copolymerization (ROIMP) of dicyclopentadiene to afford the crosslinked PDCPD. In the crosslinked PDCPD networks, N-coordinated cyclic boronic ester bonds are integrated. It is found that the as-obtained PDCPD networks displayed the excellent reprocessing properties. In the meantime, the fracture toughness is significantly improved. Owing to the inclusion of N-coordinated cyclic boronic ester bonds, the modified PDCPDs have the thermal stability much superior to plain PDCPD. The results reported in this work demonstrate that PDCPD can successfully be transformed into the vitrimers via the introduction of N-coordinated cyclic boronic ester bonds.