Polybenzoxazines, PBA-a or P(BA-a)s, are an emerging class of thermosetting resins that display excellent properties such as high glass transition temperatures, low water absorption and flammability, near-zero volumetric cure shrinkage, and very good dielectric, thermal, and mechanical properties even at modest polymer molecular weights. Functionalizing PBA-a with other polymers offers unique opportunities for creating hybrid materials with stable, tuned physical, chemical, and mechanical properties. The high temperatures required for the thermal ROP of benzoxazines have in part contributed to the lack of widespread deployment of these resins into various industries. The solubility, polymerization, and the macromolecular structure of cured blends of BPA-based benzoxazine (BA-a) monomers in sulfonyl-ester materials are studied. In many cases, BA-a monomer can be homogeneously dispersed in polymers with a wide loading range (∼40-100 wt %). In tosylated polymer / BA-a blends, the cure temperature for the ring-opening polymerization of BA-a can be up to 50 °C less than that of pure BA-a or other control materials. Advance spectroscopic techniques (including TGA-FTIR and TGA-MS) are used to elucidate the mechanism of polymerization. The tuning of chemical, physical, thermal and mechanical properties of the graft copolymers with the blend composition in also demonstrated.

Hybrid materials from the cure accelerated grafting thermal ring-opening polymerization of benzoxazines in blends with sulfonyl-ester materials

ACS Spring 2022

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