Network homogeneity on linear and nonlinear viscoelasticity of polyethylene terephthalate vitrimers

Designing network topology with tunable dynamics and rheology behaviors is the key for vitrimers applications. In this study, PET vitrimers with varying crosslinking density and network homogeneity were created by using different Mw of precursors and branching agents (catalysts). Our results show that the dynamic network formed by propane-type branching agent such as 1,3-bis[tris(hydroxymethyl) methylamino] propane (BIS-TRIS propane), is more uniform due to steric hindrance effect compared to 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol (BIS-TRIS). The thermal behavior of PET vitrimers was investigated by non-isothermal experiments, including glass transition and crystallization process. In particular, rheology behavior is sensitive to network structure and bond exchange process. The linear viscoelasticity (LVE) region of PET vitrimers is characterized by constructed pseudo-master curves that are guided by two distinct relaxation mechanisms: Rouse-type relaxation of strands and terminal relaxation of the network. Each relaxation mechanism is associated with a unique activation energy. The mechanical and processing properties of the PET vitrimers are reflected in their plateau modulus and characteristic relaxation time, which varies depending on the network topology. Based on the LVE analysis, we further investigated nonlinear rheology of PET vitrimers under extensional flow. Our results indicate that PET vitrimers exhibit significant strain hardening behavior, but display distinct stretching trends, corresponding to polymer melts' ductility. The ductility of materials decreases with a decrease in precursor's molecular weight (Mw), but improved with enhanced network homogeneity. Therefore, the crosslinking density and network homogeneity of dynamic network can be selectively tailored using appropriate precursors and branching agents to meet various industrial applications.