Synthesis of bio-based polyimine networks with flame-retardancy, acid-degradablility, and reprocessability

Abstract

Conventional thermosetting materials lack of reprocessability, acid-degradability, and fire-safety, which limit the further popularization and application of materials. In this study, a hexasubstituted cyclotriphosphazene (HVP) was synthesized from abundant renewable vanillin, and then combined with two bio-based amines (castor oil polyamine and furan-derived diamine) to establish polyimine networks through a condensation reaction between amino groups and aldehyde groups. Five bio-based polyimine thermoset networks (FA-0, FA-25, FA-50, FA-75, and FA-100) were prepared with an ammonia-formaldehyde ratio of 1:1, and varying the ratio of the two bio-based amines allowed for regulating the final mechanical properties (from tough plastic-like to hard plastic-like) and flame resistance of the materials. Among the five experimental samples, FA-100 exhibited the best physical properties stress and Tg of 28.47 MPa and 63.8 °C, respectively. FA-100 networks also showed the best flame retardant properties (LOI, 28.8 vol/%). Furthermore, due to the dynamic imine bonds in the polymer network, the material could be recycled under hot pressing conditions (120 °C and 15 MPa). Meanwhile, the monomer HVP could be recovered under mild acidic circumstances. These thermosetting polyimine networks provide a new avenue for the development of multifunctional bio-based polymer materials for practical applications.