Is a Vitrimer with a High Glass Transition Temperature Available? A Case Study on Rigid Polyimides Cross‐Linked with Dynamic Ester Bonds

Abstract Vitrimers, possessing associative covalent adaptable networks, are cross‐linked polymers exhibiting malleable (glass‐like) feature and recyclable and reprocessable (thermoplastics‐like) properties. The dynamic behaviors of vitrimer are dependent on both chain/molecular mobility (glass transition temperature, T g ) and dynamic bond‐exchanging reaction rate (topology freezing transition temperature, T v ). This work aims on probing the effect of high T g on the stress relaxation and physical recyclability of vitrimers, employing a polyimide cross‐linked with dynamic ester bonds ( T g : 310 °C) as the example. Due to its high T g and chain rigidity, the cross‐linked polyimide does not exhibit a high extent of stress relaxation behavior at 320 °C (10 °C above its T g ), even though the temperature is much higher than the hypothetical T v . While raising the processing temperature to 345 °C, the cross‐linked polyimide exhibits a stress relaxation time of about 3300 s and physical malleability. Nevertheless, side reactions may occur in the recycling and reprocessing process under the harsh condition (high temperature and high pressure) to alter the thermal properties of the recycled sample. The diffusion control plays a critical role on the topography transition of a vitrimer having a high T g . The T g ceiling is noticeable for developments of vitrimers.