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

Journal Article · · Angewandte Chemie (International Edition)
 [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)
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1605694
Alternate ID(s):
OSTI ID: 1575101
Journal Information:
Angewandte Chemie (International Edition), Vol. 59, Issue 2; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

References (31)

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
conformational entropy
mechanical properties
poly(diketoenamie)
rheology
vitrimers