Common linear polymers are known to undergo phase changes at the glass-transition temperature (Tg) and the melting point (Tm). In recent years, it has also been shown that molecules with long aliphatic side chains can give rise to a backbone-independent melting phenomenon, known as nanophase separation. This effect describes the self-assembly — independent of the polymer backbone — of alkyl side chains into semi-crystalline nanostructures. This work presents optimized, gram scale synthesis routes for dodecyl and octadecyl acrylamide and their respective homopolymers. Differential scanning calorimetry (DSC) experiments detected a broad endothermal signal for poly(n-dodecyl acrylamide) at − 29 °C and a narrower, more intense signal for poly(n-octadecyl acrylamide) at 34 °C. These signals indicate the nanophase separation TM of the alkyl side chains. We undertook the first temperature-controlled infrared spectroscopy investigations of these materials revealing a clear hypsochromic shift of the C–H stretching signals above TM and the amide I signal shifts that occurred only above and below Tg. These results provide further evidence, that the side chains act independently of the polymer backbone and show that infrared spectroscopy is a powerful tool for monitoring conformational changes in polymer side chains.
Graphical abstract
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.