Photoresponsive Spiropyran and DEGMA‐Based Copolymers with Photo‐Switchable Glass Transition Temperatures

Herein, novel photoresponsive spiropyran (SP)-based P(DEGMA-co-SpMA) copolymers with variable percentages of SP fractions are synthesized. The SP group present in these polymers exhibited the abilities of reversible photoisomerism. Their photoresponsive, structural, and thermal properties have been investigated and compared using various characterization techniques. These light-responsive copolymers are found to exhibit photoswitchable glass transition temperature (T$_g$), high thermal stability (T$_d$ > 250°C), instant photochromism as well as fluorescence upon exposure to UV light. It is demonstrated that the T$_g$ of these synthesized polymers increased when irradiated with UV light (λ = 365 nm), as a consequence of the photoisomerization of incorporated SP groups into their merocyanine form. This increase in T$_g$ is attributed to an increase in polarity and a decrease in the overall entropy of the polymeric system when it switches from the ring-closed SP form (less-ordered state) to the ring-opened merocyanine form (more-ordered state). Therefore, such polymers with a unique feature of phototunable glass transition temperatures provide the possibility to be integrated into functional materials for various photoresponsive applications.