Raman Microspectroscopy Study of the Hydrolytic Degradation of Polyanhydride Network Polymers

Raman microspectroscopy was employed in this work to study the degradation of a polyanhydride network polymer synthesized from 4-pentenoic anhydride and pentaerythritol tetrakis(3-mercaptopropionate) monomers in order to illustrate the utility of this method and improve the understanding of the polyanhydride degradation and erosion. Disk-shaped polymer samples were immersed in buffer solutions for different periods of time, and hydrolytic degradation was monitored spatially and temporally via kinetic Raman studies at various depths of penetration into the samples. Erosion, meanwhile, was monitored via mass loss measurements. Dispersive Raman microspectroscopy is shown to be a particularly valuable tool for the study of the hydrolytic degradation of these materials. It confirms that these thiol-ene polyanhydrides are indeed surface eroding, while also revealing that degradation starts to occur at the core of samples on a short time scale (less than 5 h). At any given degradation time, there is a concentration gradient of the unreacted anhydride, with the unreacted anhydride concentration increasing from the outer edge to the center of the polymer samples. Further, the anhydride functionality is found to decrease approximately linearly with degradation time at all depths in the samples, though the degradation rate does appear to increase slightly as degradation occurs.