Epoxy-based
elastomers with remarkable flexibility have garnered
attention due to their versatility in various applications, including
sensors, smart fabrics, nanocomposites, and thermally conductive composite
materials. In these studies, the selection of an appropriate hardener
is crucial to imparting elastomeric properties to epoxy. Among the
various available hardeners, thiol-based hardeners present notable
advantages. First, they facilitate rapid curing at low temperatures
via an epoxy–thiol click reaction. Second, the flexibility
of the C–S bonds enables glass transition near room temperature.
Despite these merits, the utilization of thiol-based hardeners in
epoxy elastomer materials remains limited, primarily due to the lack
of a well-established structure–property relationship between
the thiol hardeners and epoxy elastomers. In this study, we carefully
examined the effect of the hardener structure on the properties of
thiol–epoxy polymers. While maintaining the structure of a
tetrafunctional thiol as a cross-linker, we varied the structure of
a bifunctional thiol to analyze its influence on the physical properties
of the resulting thiol–epoxy material. Factors such as the
presence or absence of an oxygen atom, the existence of a ring structure,
the presence or absence of aromatics, and the geometric shape of the
hardener all influenced the mechanical properties, such as modulus,
stress, and toughness. Notably, the structure of the bifunctional
hardener allowed precise control over the glass transition temperature
of the thiol–epoxy material near room temperature, resulting
in distinct mechanical behaviors (elastic or plastic) at room temperature.
Based on these findings, we successfully developed a thiol–epoxy
material exhibiting elastomeric behavior at room temperature and shape
memory characteristics at temperatures close to room temperature (e.g.,
40 °C).