Structure and Thermal Analyses of MAA‐Grafted Silk Fiber Using DSC and ¹³C Solid‐State NMR

Summary: By using DSC, 13 C CP/MAS NMR and SEM, we studied the physical properties and chemical structure of silk fibers grafted with methacrylamide (MAA). At a given MAA concentration, the inverse of fiber weight gain linearly increased with increasing square root of the initiator concentration, and at a given initiator concentration the fiber weight gain increased with increasing MAA concentration. 13 C CP/MAS NMR demonstrated that the primary and secondary structure remained unchanged, regardless of MAA grafting, implying the poor compatibility and the lack of new additional hydrogen bonding between the silk fiber and the MAA graft polymer. The degree of grafting in MAA‐grafted silk fiber (the accurate amount of actually loaded MAA polymer within the fiber matrix) can be evaluated from determination of the ratio of heat capacities calculated from two individual endothermic DSC peaks of silk fibroin and MAA polymer. The major endothermic peaks attributable to thermal degradation of the silk fiber and MAA graft polymer shifted to a higher temperature with increasing fiber weight gain by grafting. These findings are useful for the industrial production of grafted silk fiber with higher thermal stability. CP/MAS spectra for poly(MAA) grafted silk and control silk fiber. magnified image CP/MAS spectra for poly(MAA) grafted silk and control silk fiber.