ABSTRACT
Invited for the cover of this issue is the group of Danqing Liu and co-workers at the University of Eindhoven University of Technology. The image depicts two-step photopolymerization-induced diffusion for the fabrication of gradient-structured dual-responsive thiol-ene networks. Read the full text of the article at 10.1002/chem.202400515.
ABSTRACT
Stimuli-responsive materials have recently gained significant attention in the field of soft robotics, sensors, and biomimetic devices. The most facile way for the fabrication of such materials remains to endow bilayer structures which are fabricated with the combination of active and passive layers. Although, easily fabricated, these structures suffer from the generation of stress points between connection areas. In this work we develop a method to create a thin film with controlled cross-link variation across its thickness. The cross-link gradient is achieved through polymerization induced diffusion of dithiol molecules in thiol-ene network. As a result, the film exhibits bending deformation upon illumination with light or exposure to a chemical solvent, thereby demonstrating dual responsiveness. Light actuation of the film is achieved via photothermal effects due to the incorporation of dye into the system which can absorb UV light and heat the network. While solvent induced actuation is due to anisotropic swelling. Furthermore, the straightforward fabrication procedure allows for the creation of more complex deformations by patterning the film using a photomask during photopolymerization.
ABSTRACT
Cholesteric liquid crystal oligomers are widely researched for their interesting thermochromic properties. However, structure-property relationships to program the thermochromic properties of these oligomers have been rarely reported. In this work, we use the versatile thiol-ene click reaction to synthesize a series of hetero-oligomers and study the impact of different compositions on the thermochromic behavior of the resulting material. Characterization of the oligomers shows significantly different rates of reaction for the monomers despite their very similar structures, which leads to oligomer compositions that do not match the original reaction feed. The oligomers are then used to produce thin near-infrared reflecting coatings. The best-performing thermochromic reflector has a room-temperature reflection band that shifts a total of 510 nanometers upon heating to 120 °C. The shift is repeatable for up to 10 times with no appreciable degradation. The room temperature reflection of the coatings is shown to be tunable not only by adjusting the chiral dopant concentration but also by the ratio of the monomers. Finally, we show that the oligomers can be chemically modified by making their reactive end groups undergo a reaction with monothiol compounds. These modifications allow for further fine-tuning of liquid crystal oligomers for heat-regulating window films, for example.
