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, Tg) and dynamic bond‐exchanging reaction rate (topology freezing transition temperature, Tv). This work aims on probing the effect of high Tg on the stress relaxation and physical recyclability of vitrimers, employing a polyimide cross‐linked with dynamic ester bonds (Tg: 310 °C) as the example. Due to its high Tg and chain rigidity, the cross‐linked polyimide does not exhibit a high extent of stress relaxation behavior at 320 °C (10 °C above its Tg), even though the temperature is much higher than the hypothetical Tv. 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 Tg. The Tg ceiling is noticeable for developments of vitrimers.