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Title: Covalent Adaptable Networks with Rapid UV Response Based on Reversible Thiol–Ene Reactions in Silicone Elastomers
PhotoCAN silicone elastomers, based on the thiol–ene reaction, exhibit rapid and reversible changes in dynamic modulus at room temperature when illuminated by UV. By combining results from magic angle spinning solid-state NMR as well as EPR and rheometry measurements, both under UV, it is concluded that the mechanical response can be attributed to a combination of dissociative, associative, and oxidation reactions. The cleavage of the C–S bonds under UV in the presence of an excess of thiyl radicals is identified as the reversible dissociative reaction responsible for abrupt drops in the storage modulus. A slower but concurrent reaction is a termination process involving thiyl radicals to form disulfide bonds. A kinetic model is developed that successfully relates the rates of the underlying reaction mechanisms to changes in the storage modulus. The results provide a basis for designing new, ambient temperature photoresponsive covalently adaptive network materials.  more » « less
Award ID(s):
2011754
PAR ID:
10500441
Author(s) / Creator(s):
; ;
Publisher / Repository:
ACS
Date Published:
Journal Name:
Macromolecules
Volume:
56
Issue:
22
ISSN:
0024-9297
Page Range / eLocation ID:
9107 to 9116
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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