Influence of Zn2+ catalyst stoichiometry on curing dynamics and stress relaxation of polyester-based epoxy vitrimer

Abstract

In the classical “covalent adaptive network” constructed by diglycidyl ether of bisphenol A (DGEBA) and crosslinking agent glutaric anhydride (GA), Zn-based catalyst greatly affects the curing crosslinking reaction and dynamic transesterification reaction. Herein, the crucial roles of Zn(Ac)2 catalyst in the curing dynamics and stress relaxation were studied. The results reveal that increasing the content of Zn(Ac)2 can significantly reduce the reaction activation energy (Eα) at initial stage, thus effectively promoting the curing crosslinking reaction. The analyses of dynamic properties suggest that although stress relation time (τ) can be shortened by increasing catalyst content, the high content of catalyst would lead a fast transesterification rate at relatively low temperature, which is adverse to the mechanical stability of vitrimer resin at operating temperature. By comparison, the vitrimer resin with modest catalyst content (mole ratio of 1:0.5:0.05) shows a highest viscous flow activation energy (Eτ), i.e., excellent dimensional stability and processability. Besides, the crosslinking density of resin was significantly affected by the content of catalyst. Since the competitive catalytic effects on curing cross-linking reaction and subsequent transesterification, the vitrimer resin of 1:0.5:0.05 exihits the highest crosslinking density (1855 mol/m3), so that it has highest Tg (79 °C) and tensile strength (72 MPa).