The influence of dynamic crosslinked topology and bond exchange on thermal properties, viscoelasticity, and foaming behavior of multibranched TPEE vitrimer

Thermoplastic polyester ether elastomer (TPEE) vitrimers with different dynamic crosslinked networks were synthesized via zinc (II) acetylacetonate-catalyzed epoxy chemistry. The effects of bond exchange within networks, characterized by number of catalytic centers per crosslink (CC), and the dynamic crosslinked topology, characterized by number of entanglement and crosslinking points per crosslink (EC), on thermal, rheological, and foaming properties of TPEE vitrimer were compared. The results show that increasing EC is more favorable for lower crystallization temperature than improving bond exchange owing to the bad structural symmetry but almost constant crystallinity owing to the branches. TPEE vitrimer with a complex dynamic crosslinked topology exhibited slow relaxation with a stronger relaxing response and steeper strain hardening than that with more bond exchanges, indicating better viscoelasticity. Moreover, the good foaming behavior of TPEE vitrimers was ascribed to the dynamic crosslinked networks, which promoted heterogeneous nucleation to increase the cell density, and strain hardening good for cell growth as it suppressed cell coalescence and rupture. Furthermore, increasing CC facilitates bond exchange, promoting more uniform heterogeneous nucleation and cell size dispersity than those afforded by a complex dynamic crosslinked topology achieved by increasing EC. The improvement of foaming behavior for TPEE vitrimer is quite different from that of branched polymer by enhancing cell growth rather than cell density.