Reprocessable Polybenzoxazine Thermosets with High Tgs and Mechanical Strength Retentions Using Boronic Ester Bonds as Crosslinkages.

Abstract

In order to obtain reprocessable polybenzoxazine thermosets with high heat resistance and mechanical strength retentions, network structures without irreversible parts were constructed via crosslinking benzoxazine oligomers using boronic ester cross-linkers. Firstly, the benzoxazine monomer containing carbon–carbon double bonds was synthesized via the Mannich reaction. After thermal ring-opening polymerization, the benzoxazine oligomer containing carbon–carbon double bonds (OBZ) was yielded. Through the thiol-ene click reaction of the OBZ and dithiol cross-linker bearing boronic ester bonds, the polybenzoxazine thermosets using boronic ester bonds as crosslinkages (OBZ-BDB) were successfully synthesized. The structures of OBZ and OBZ-BDB were characterized by SEC, 1H NMR, and FT-IR measurements. Reprocessing experiments showed that OBZ-BDB has remarkable reprocessability. The retention rates of the tensile strengths through three generations of reprocessing were 98%, 95%, and 84%, respectively. Meanwhile, OBZ-BDB cross-linked by boronic ester bonds had brilliant thermal properties. The Tg of the original OBZ-BDB was 224 °C. With the increase of the reprocessing generations, the Tgs basically remained unchanged.