Facile Preparation of Polyimine Vitrimers with Enhanced Creep Resistance and Thermal and Mechanical Properties via Metal Coordination
Sheng Wang, Songqi Ma,* Qiong Li, Xiwei Xu, Binbo Wang, Kaifeng Huang, Yanlin liu, and Jin Zhu
摘要：Vitrimers undergoing dynamic bond exchange enable reprocessing and recycle of thermosets. However, vitrimers are susceptible to creep, leading to their poor dimensional stability, which limits their applications. Here, a facile method via integration of metal complexes was utilized to address this issue, and cross-linked polyimine was selected as an example of vitrimer. Three different metal complexes were introduced into a polyimine vitrimer via a onepot preparation involving the formation of metal complexes and crosslinking of polyimine. The addition of 0.5 mol % Cu2+ relative to imine bond reduced creep degree from 30% to 20% at 60 °C, and the creep resistance was enhanced with increasing Cu2+ content. Loading 5 mol % Cu2+ increased the initial creep temperature from 60 to about 100 °C and raised the Arrhenius activation energy (Ea) for stress relaxation from 52.3 to 67.7 kJ mol-1. The ability of different metal complexes to suppress creep followed the order of Fe3+ > Cu2+ > Mg2+, and the initial creep temperature reached around 120 °C for vitrimer with 5 mol % of Fe3+. Meanwhile, the polyimine-metal complex vitrimers still exhibited excellent reprocessing recyclability. Moreover, the introduction of coordination structures enhanced the thermal and mechanical properties, solvent, and acid resistance. Thus, metal coordination is an efficient approach to achieve high-temperature creep resistance, excellent thermal and mechanical properties, and chemical stability for vitrimers based on the Schiff base.
論文鏈接： https://pubs.acs.org/doi/10.1021/acs.macromol.0c00036