In Situ Network Formation in PBT Vitrimers via Processing‐Induced Deprotection Chemistry

Although the network dynamics and mechanical properties of poly(butylene terephthalate) vitrimers can to some extent be controlled via chemical and physical approaches, it remains a challenge to be able to process PBT vitrimers with the same processing conditions via, for example, injection molding as neat PBT. Here, it is shown that the use of protected pentaerythritol as a latent cross‐linker and the use of a Zn(II) transesterification catalyst allows for the in situ dynamic network formation in PBT during processing, with a delayed onset of gelation. This process can be controlled by adjusting the processing temperature, (protected) cross‐linker content, and the type of protection group. This solvent‐free deprotection strategy opens the way to high production rates of PBT vitrimer products via injection molding with the combination of low viscosity during processing and vitrimer characteristics in the final product. Poly(butylene terephthalate) vitrimers have a high melt strength and can be reprocessed, repaired, and recycled and as such allow for the use of additional processing technologies and applications at higher temperatures. In situ network formation directed by protection–deprotection chemistry paves the way for fast processing using current extrusion or injection molding equipment of PBT vitrimers.