Mechanically activated, catalyst-free polyhydroxyurethane vitrimers.
Vitrimers are polymer networks whose cross-links undergo associative exchange processes at elevated temperature, usually in the presence of an embedded catalyst. This design feature enables the reshaping of materials with mechanical properties similar to thermoset resins. Here we report a new class of vitrimers consisting of polyhydroxyurethanes (PHUs) derived from six-membered cyclic carbonates and amines. PHU networks relax stress and may be reprocessed at elevated temperature and pressure in the absence of an external catalyst. The as-synthesized networks exhibit tensile properties comparable to those of leading thermosets and recover ca. 75% of their as-synthesized values following reprocessing. Stress relaxation occurs through an associative process involving nucleophilic addition of free hydroxyl groups to the carbamate linkages and exhibits an Arrhenius activation energy of 111 ± 10 kJ/mol, which is lower than that observed for molecular model compounds (148 ± 7 kJ/mol). These findings suggest that transcarbamoylation is activated by mechanical stress, which we attribute, on the basis of DFT calculations, to the twisting of N lone pairs out of conjugation with the carbonyl π orbitals. PHU vitrimers are a promising new class of repairable networks because of their outstanding mechanical properties, avoidance of toxic isocyanate monomers, and catalyst-free repair processes.
Department of Chemistry and Chemical Biology, Cornell University , Baker Laboratory, Ithaca, New York 14853-1301, United States.
David J
DJ
Fortman
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
Jacob P
JP
Brutman
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
Christopher J
CJ
Cramer
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
Marc A
MA
Hillmyer
Department of Chemistry and Chemical Biology, Cornell University , Baker Laboratory, Ithaca, New York 14853-1301, United States.
William R
WR
Dichtel