Abstract
Network synthesis strategies are critical in determining the properties of liquid crystal elastomers (LCEs), making their selection essential for tailoring material performance. This study systematically compares chain extension and chain transfer approaches to identify key structural factors governing LCE behavior. By assessing how the chemical nature and length of liquid crystal oligomers in chain extension, as well as the proportion of pendant thiols in chain transfer, influence material properties, we establish cross-linking density, mesogen content, and mesogen distribution as key structural factors impacting LCE performance across both synthesis routes. To illustrate the practical significance of these findings, a LCE bilayer with shape-memory behavior is fabricated using two LCE networks with distinct thermomechanical properties, demonstrating controlled rolling deformation upon heating. Overall, this study provides a framework for designing LCEs with tailored properties by selecting the appropriate synthesis route.