Study on Thermal Oxygen Aging Characteristics and Degradation Kinetics of PMR350 Resin

The thermal stability and aging kinetics of polyimides have garnered significant research attention. As a newly developed class of high thermal stability polyimide, the thermal aging characteristics and degradation kinetics of phenylene-capped polyimide prepolymer (PMR350) have not yet been reported. In this article, the thermo-oxidative stability of PMR350 was investigated systematically. The thermal degradation kinetics of PMR350 resin under different atmospheres were also analyzed using the Flynn-Wall-Ozawa method, the Kissinger-Akahira-Sunose method, and the Friedman method. Thermogravimetric analysis (TGA) results revealed that the 5% thermal decomposition temperature (Td5%) of PMR350 in a nitrogen atmosphere was 29 °C higher than that in air, and the maximum thermal degradation rate was 0.0025%/°C, which is only one-seventh of that observed in air. Isothermal oxidative aging results indicated that the weight loss rate of PMR350 and the time-dependence relationship follow a first-order exponential growth function. PMR350 resin thermal decomposition reaction under air atmosphere includes one stage, with a degradation activation energy of approximately 57 kJ/mol. The reaction model g(α) fits the F₂ model, and the integral form is given by g(α) = 1/(1 - α). In contrast, the thermal decomposition reaction under a nitrogen atmosphere consists of two stages, with degradation activation energies of 240 kJ/mol and 200 kJ/mol, respectively. The reaction models g(α) correspond to the A₂ and D₃ models, with the integral forms represented as g(α) = [-ln(1 - α)]² and g(α) = [1 - (1 - α)^1/3]² due to the oxygen accelerating thermal degradation from multiple perspectives. Moreover, PMR350 resin maintained high hardness and modulus even after thermal aging at 350 °C for 300 h. The results indicate that the resin exhibits excellent resistance to thermal and oxygen aging. This study represents the first systematic analysis of the thermal stability characteristics of PMR350 resin, offering essential theoretical insights and data support for understanding the mechanisms of thermal stability modification in PMR350 and its engineering applications.