Structural effects on the reprocessability and stress relaxation of crosslinked polyhydroxyurethanes

David J. Fortman, Jacob P. Brutman, Marc A. Hillmyer, William R. Dichtel

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103 Scopus citations


Crosslinked polyhydroxyurethane (PHU) networks synthesized from difunctional six-membered cyclic carbonates and triamines are reprocessable at elevated temperatures through transcarbamoylation reactions. Here we study the structural effects on reprocessability and stress relaxation in crosslinked PHUs. Crosslinked PHUs derived from bis(five-membered cyclic carbonates) are shown to decompose at temperatures needed for reprocessing, likely via initial reversion of the PHU linkage and subsequent side reactions of the liberated amine and cyclic carbonate. Therefore, several six-membered cyclic carbonate-based PHUs with varying polymer backbones and crosslink densities were synthesized. These networks show large differences in the Arrhenius activation energy of stress relaxation (from 99 to 136 kJ/mol) that depend on the network structure, suggesting that transcarbamoylation reactions may be highly affected by both chemical and mechanical effects. Furthermore, all crosslinked PHUs derived from six-membered cyclic carbonates show mechanical properties typical of thermoset polymers, but recovered as much as 80% of their as-synthesized tensile properties after elevated temperature compression molding. These studies provide significant insight into factors affecting the reprocessability of PHUs and inform design criteria for the future synthesis of sustainable and repairable crosslinked PHUs.

Original languageEnglish (US)
Article number44984
JournalJournal of Applied Polymer Science
Issue number45
StatePublished - Dec 5 2017

Bibliographical note

Funding Information:
The authors thank Christopher Cramer for helpful discussions. This research was supported by the National Science Foundation (NSF) through the Center for Sustainable Polymers (CHE-1413862). This research made use of the Cornell Center for Materials Research User Facilities, which are supported by the NSF (DMR-1120296), the Materials Characterization and Imaging Facility, which receives support from the MRSEC Program (NSF DMR-1121262) of the Materials Research Center at Northwestern University, and the Integrated Molecular Structure Education and Research Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF NNCI-1542205), the State of Illinois, and the International Institute for Nanotechnology.

Publisher Copyright:
© 2017 Wiley Periodicals, Inc.


  • mechanical properties
  • polyurethanes
  • recycling
  • thermal properties
  • thermosets


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