Fast Upcycling of Poly(ethylene terephthalate) into Catalyst-Free Vitrimers

We reported a catalyst-free technique to fabricate transesterification-based poly(ethylene terephthalate) (PET) vitri-mers via melt reacting PET with N,N '-tetraglycidyldiaminodi-phenyl methane (TGDDM) in several minutes. We investigated the effect of TGDDM content on the reaction mechanism and chemical structure of the final products in detail. At low TGDDM content (<= 0.5 wt %), branched thermoplastic PET was obtained by the chain-extension reaction between carboxyl groups of PET and epoxy groups of TGDDM. At medium TGDDM content (0.7-1.0 wt %), PET vitrimers with relatively low cross-link density were achieved through the cross-linking reaction between original carboxyl plus hydroxyl groups of PET and epoxy groups of TGDDM. At high TGDDM content (1.2-2.0 wt %), soluble chain-extended products were first formed through reacting original carboxyl and hydroxyl groups of PET with part of epoxy groups of TGDDM, and PET vitrimers were then obtained after the excess epoxy groups were consumed by the newly formed functional groups, which were generated by thermal decomposition of ester groups of PET under catalyzation of tertiary amines of TGDDM moieties. The cross-linked network structure endowed the PET vitrimers with enhanced heat resistance and creep resistance. The obtained PET vitrimers could relax stress rapidly and showed excellent processability and weldability, owing to the fast transesterification between hydroxyl and ester groups under catalyzation of internal tertiary amines. We believe that the facile fabrication technique showed great potentiality for upcycling of PET into vitrimers in large-scale production.

Automated summary

We developed a catalyst-free technique for the synthesis of transesterification-based PET vitrimers, using TGDDM as a reactant in a melt reaction. The TGDDM content was found to affect the reaction mechanism and chemical structure of the final products. At different TGDDM contents, different structures of PET vitrimers were obtained, which exhibited enhanced heat resistance and creep resistance. The facile fabrication technique showed great potential for upcycling PET into vitrimers in large-scale production.