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Title: Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

Abstract

Control of equilibrium and non-equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (Tg), both Tg and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MW of flexible linear segments but increases with increasing MW of stiff segments. Finally, vitrimer reconfigurability is therefore influenced not only by the energetics of bond exchange for a given network density, but also the entropy of polymer chains within the network.

Authors:
 [1];  [2];  [2];  [2];  [3];  [2];  [3];  [4]; ORCiD logo [2]
  1. Beijing Univ. of Chemical Technology (China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  4. Beijing Univ. of Chemical Technology (China); Univ. of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
OSTI Identifier:
1605694
Alternate Identifier(s):
OSTI ID: 1575101
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 2; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conformational entropy; mechanical properties; poly(diketoenamie); rheology; vitrimers

Citation Formats

He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., and Helms, Brett A.. Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium. United States: N. p., 2020. Web. https://doi.org/10.1002/anie.201912223.
He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., & Helms, Brett A.. Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium. United States. https://doi.org/10.1002/anie.201912223
He, Changfei, Christensen, Peter R., Seguin, Trevor J., Dailing, Eric A., Wood, Brandon M., Walde, Rebecca K., Persson, Kristin A., Russell, Thomas P., and Helms, Brett A.. Tue . "Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium". United States. https://doi.org/10.1002/anie.201912223. https://www.osti.gov/servlets/purl/1605694.
@article{osti_1605694,
title = {Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium},
author = {He, Changfei and Christensen, Peter R. and Seguin, Trevor J. and Dailing, Eric A. and Wood, Brandon M. and Walde, Rebecca K. and Persson, Kristin A. and Russell, Thomas P. and Helms, Brett A.},
abstractNote = {Control of equilibrium and non-equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (Tg), both Tg and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MW of flexible linear segments but increases with increasing MW of stiff segments. Finally, vitrimer reconfigurability is therefore influenced not only by the energetics of bond exchange for a given network density, but also the entropy of polymer chains within the network.},
doi = {10.1002/anie.201912223},
journal = {Angewandte Chemie (International Edition)},
number = 2,
volume = 59,
place = {United States},
year = {2020},
month = {1}
}

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