Entropy-controlled cross-linking in linker-mediated vitrimers

@article{Lei2020EntropycontrolledCI,
  title={Entropy-controlled cross-linking in linker-mediated vitrimers},
  author={Qun-li Lei and Xiuyang Xia and Juan Yang and Massimo Pica Ciamarra and Ran Ni},
  journal={Proceedings of the National Academy of Sciences},
  year={2020},
  volume={117},
  pages={27111 - 27115}
}
  • Qun-li LeiXiuyang Xia R. Ni
  • Published 14 July 2020
  • Materials Science, Biology
  • Proceedings of the National Academy of Sciences
Significance The recently developed linker-mediated vitrimers based on metathesis reactions offer new possibilities of processing cross-linked polymers with high mechanical performance in industry, while the design principle remains unknown. Here we propose a theoretical framework for describing the system of linker-mediated vitrimers, in which entropy is found to play a dictating role. Our mean field theory agrees quantitatively with computer simulations, and provides guidelines for the… 
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References

SHOWING 1-10 OF 36 REFERENCES

Relationship between Reaction Kinetics and Chain Dynamics of Vitrimers Based on Dioxaborolane Metathesis

Processability of vitrimers strongly relies on the temperature dependence of viscosity. In this study, we analyzed temperature-dependent viscoelasticity of vitrimers based on the dioxaborolane

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis

The metathesis of dioxaborolanes is reported, which is rapid and thermally robust, and used to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding.

Vitrimers: Permanently crosslinked polymers with dynamic network topology

Phase Separation and Self-Assembly in Vitrimers: Hierarchical Morphology of Molten and Semicrystalline Polyethylene/Dioxaborolane Maleimide Systems

Vitrimers are a class of polymers that flow when heated but are insoluble. Vitrimers are made of covalent networks with dynamic links and/or cross-links that undergo an associative exchange reaction.

Making insoluble polymer networks malleable via olefin metathesis.

By introducing a very low level of the Grubbs' second-generation Ru metathesis catalyst, a chemically cross-linked polybutadiene network becomes malleable at room temperature while retaining its insolubility.

Linear visocelasticity and flow of self-assembled vitrimers: The case of a polyethylene/dioxaborolane system

For vitrimer systems obtained by dynamic cross-linking of polymer chains, incompatibility effects between the cross-links and polymer backbone can lead to microphase separation, resulting in a

Dynamic covalent chemistry in polymer networks: a mechanistic perspective

A selection of dynamic chemistries is highlighted, with a focus on the reaction mechanisms of molecular network rearrangements, and on how mechanistic profiles can be related to the mechanical and

Heat‐ or Water‐Driven Malleability in a Highly Recyclable Covalent Network Polymer

The polyimine is presented, which fundamentally behaves like a classic thermoset at ambient conditions yet can be reprocessed by application of either heat or water, and is thus the fi rst reported Covalent network polymers, which offer robust mechanical properties, generally lack the ability to be recycled.

Understanding, predicting, and tuning the fragility of vitrimeric polymers

The microstructure–fragility link in vitrimeric networks, a novel type of high-performance polymers with unique bond-swapping functionality and unusual glass-forming behavior, is explained and provides a first-principles–based platform for designing amorphous materials with an on-demand dynamic response.