Abstract
Recently developed linker-mediated vitrimers based on metathesis of dioxaborolanes with various commercially available polymers have shown both good processability and outstanding performance, such as mechanical, thermal, and chemical resistance, suggesting new ways of processing cross-linked polymers in industry, of which the design principle remains unknown [M. Röttgeret al.,Science356, 62–65 (2017)]. Here we formulate a theoretical framework to elucidate the phase behavior of the linker-mediated vitrimers, in which entropy plays a governing role. We find that, with increasing the linker concentration, vitrimers undergo a reentrant gel–sol transition, which explains a recent experiment [S. Wu, H. Yang, S. Huang, Q. Chen,Macromolecules53, 1180–1190 (2020)]. More intriguingly, at the low temperature limit, the linker concentration still determines the cross-linking degree of the vitrimers, which originates from the competition between the conformational entropy of polymers and the translational entropy of linkers. Our theoretical predictions agree quantitatively with computer simulations, and offer guidelines in understanding and controlling the properties of this newly developed vitrimer system.
Funder
Ministry of Education - Singapore
Nanyang Technological University
A*STAR | Science and Engineering Research Council
Publisher
Proceedings of the National Academy of Sciences
Cited by
17 articles.
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