Diarylethene‐functionalized liquid‐crystalline elastomers (DAE‐LCEs) containing thiol‐anhydride bonds were prepared and shown to undergo reversible, reprogrammable photoinduced actuation. Upon exposure to UV light, a monodomain DAE‐LCE generated 5.5 % strain. This photogenerated strain was demonstrated to be optically reversible over five cycles of alternating UV/Visible light exposure with minimal photochrome fatigue. The incorporation of thiol‐anhydride dynamic bonds allowed for retention of actuated states. Further, re‐programming of the nematic director was achieved by heating above the temperature for bond exchange to occur (70 °C) yet below the nematic‐to‐isotropic transition temperature (100 °C) such that order was maintained between mesogens. The observed thermal stability of each of the diarylethene isomers of over 72 h allowed for decoupling of photo‐induced processes and polymer network effects, showing that both polymer relaxation and back‐isomerization of the diarylethene contributed to LCE relaxation over a period of 12 hours after actuation unless bond exchange occurred.
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Dynamic liquid crystal elastomers (LCEs) are a class of polymer networks characterized by the inclusion of both liquid crystalline monomers and dynamic covalent bonds. The unique properties realized through the combination of these moieties has produced a plethora of stimuli‐responsive materials to address a range of emerging technologies. While previous works have studied the incorporation of different dynamic bonds in LCEs, few (if any) have studied the effect of the specific placement of the dynamic bonds within an LCE network. A series of dynamic LCE networks were synthesized using a generalizable approach that employs a tandem thiol‐ene/yne chemistry which allows the location of the dynamic disulfide bond to be varied while maintaining similar network characteristics. When probing these systems in the LC regime, the thermomechanical properties were found to be largely similar. It is not until elevated temperatures (160–180 °C) that differences in the relaxation activation energies of these systems begin to materialize based solely on differences in placement of the dynamic bond throughout the network. This work demonstrates that through intentional dynamic bond placement, stress relaxation times can be tuned without affecting the LCE character. This insight can help optimize future dynamic LCE designs and achieve shorter processing times.
more » « less- Award ID(s):
- 2011854
- NSF-PAR ID:
- 10507259
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Journal of Polymer Science
- Volume:
- 62
- Issue:
- 5
- ISSN:
- 2642-4150
- Page Range / eLocation ID:
- 907 to 915
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Diarylethene‐functionalized liquid‐crystalline elastomers (DAE‐LCEs) containing thiol‐anhydride bonds were prepared and shown to undergo reversible, reprogrammable photoinduced actuation. Upon exposure to UV light, a monodomain DAE‐LCE generated 5.5 % strain. This photogenerated strain was demonstrated to be optically reversible over five cycles of alternating UV/Visible light exposure with minimal photochrome fatigue. The incorporation of thiol‐anhydride dynamic bonds allowed for retention of actuated states. Further, re‐programming of the nematic director was achieved by heating above the temperature for bond exchange to occur (70 °C) yet below the nematic‐to‐isotropic transition temperature (100 °C) such that order was maintained between mesogens. The observed thermal stability of each of the diarylethene isomers of over 72 h allowed for decoupling of photo‐induced processes and polymer network effects, showing that both polymer relaxation and back‐isomerization of the diarylethene contributed to LCE relaxation over a period of 12 hours after actuation unless bond exchange occurred.
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