Characterization of Polymer Molecular Weight Distribution by NMR Diffusometry: Experimental Criteria and Findings

NMR diffusometry finds useful applications in characterizing molecular weight (M) and molecular weight distribution (MWD) for polymers due to its unique advantages in generic detection, chemical selectivity, and quantitation. Here, we present a fundamental study to explore how the condition of diffusion measurement impacts the determined MWD. We use the critical dilute concentration C_dilute^* to explicitly delineate the boundary of the sufficiently dilute condition, below which chain interactions have a negligible impact on polymer diffusion. We present solid evidence to validate the postulated theory that links C_dilute^* to molecular weight, polydispersity, and chain conformation. Quantitative analysis reveals the consequence of violating the sufficiently dilute condition with M/MWD characterization. These findings provide useful guidance for M/MWD characterization by NMR diffusion and help to rationalize the data disparity that exists in the literature. The results further provide new insights into the interplay between chain conformations and diffusion for globular structure, such as proteins, and provide a different approach toward characterizing polymer architecture and molecular weight.