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Abstract 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.
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Coupled bond dynamics alters relaxation in polymers with multiple intrinsic dissociation rates
Dynamic networks containing multiple bond types within a continuous network grant engineers another design parameter – relative bond fraction – by which to tune storage and dissipation of mechanical energy. However, the mechanisms governing emergent properties are difficult to deduce experimentally. Therefore, we here employ a network model with prescribed fractions of dynamic and stable bonds to predict relaxation characteristics of hybrid networks. We find that during stress relaxation, predominantly dynamic networks can exhibit long-term moduli through conformationally inhibited relaxation of stable bonds due to exclusion interactions with neighboring chains. Meanwhile, predominantly stable networks exhibit minor relaxation through non-affine reconfiguration of dynamic bonds. Given this, we introduce a single fitting parameter, ξ , to Transient Network Theory via a coupled rule of mixture, that characterizes the extent of stable bond relaxation. Treating ξ as a fitting parameter, the coupled rule of mixture's predicted stress response not only agrees with the network model's, but also unveils likely micromechanical traits of gels hosting multiple bond dissociation timescales.
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- Award ID(s):
- 2029699
- PAR ID:
- 10407377
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 19
- Issue:
- 15
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 2716 to 2725
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3SM00014A
