Understanding the Thermal Degradation Mechanism of High-Temperature-Resistant Phthalonitrile Foam at Macroscopic and Molecular Levels.

Polymer foam, a special form of polymer, usually demonstrates some unexpected properties that rarely prevail in the bulky polymer. Studying the thermal degradation behavior of a specific polymer foam is important for its rational design, quick identification, objective evaluation, and industrial application. The present study aimed to discover the thermal degradation mechanism of high-temperature-resistant phthalonitrile (PN) foam under an inert gas atmosphere. The macroscopic thermal decomposition of PN foam was carried out at the cost of size/weight loss, resulting in an increasing number of open cells with pyrolyzation debris. Using the TGA/DTG/FTIR/MS technique, it was found that PN foam involves a three-stage thermal degradation mechanism: (I) releasing gases such as H2O, CO2, and NH3 generated from azo-containing intermediate decomposition and these trapped in the closed cells during the foaming process; (II) backbone decomposition from C-N, C-O, and C-C cleavage in the PN aliphatic chain with the generation of H2O, CO2, NH3, CO, CH4, RNH2, HCN, and aromatic gases; and (III) carbonization into a final N-hybrid graphite. The thermal degradation of PN foam was different from that of bulky PN resin. During the entire pyrolysis of PN foam, there was a gas superposition phenomenon since the release of the decomposition volatile was retarded by the closed cells in the PN foam. This research will contribute to the general understanding of the thermal degradation behavior of PN foam at the macroscopic and molecular levels and provide a reference for the identification, determination, and design of PN material.

Large-Scale Preparation of Uniform Millet Bread-like Durable Benzoxazine-Phthalonitrile Foam with Outstanding Mechanical and Thermal Properties.

It is essentially important to develop durable polymer foams for services in high-temperature conditions. The current study reported the preparations and properties of a high-performance benzoxazine-phthalonitrile (BZPN) foam by utilizing azodicarbonamide and tween-80 as the blowing agent and stabilizer, respectively. Rheological and curing studies indicated that the appropriate foaming temperature for BZPN foam is below 180 °C, and its foaming viscosity window is below 20 Pa·s. Guided by these results, uniform millet bread-like BZPN foams with decimeter leveling size were successfully realized, suggesting the high prospect of large-scale production. The structural, mechanical, and thermal properties of BZPN foams were then investigated in detail. BZPN foam involves a hierarchical fracture mechanism during the compressive test, and it shows a high compression strength of over 6 MPa. During a burning test over 380 °C, no visible smoke, softening, or droplet phenomena appeared and the macroscopic structure of BZPN foam was well maintained. Mechanically robust, flame-retardant, and uniform large-size BZPN foam are promising light durable materials with high service temperatures, i.e., as filling materials even in a very narrow pipette.