PFG-NMR Studies of Linear and Dendritic Polymers

Diffusion coefficients were measured by pulsed-field gradient NMR for low molecular weight linear polystyrenes in THF and for a broader molecular weight range of linear polystyrenes in chloroform and for PAMAM dendrimers up to generation methanol. Radii were calculated from the measured diffusion coefficients using the Stokes-Einstein relationship. The linear polystyrenes displayed a relationship between radius and molecular weight that followed the expected power law. From simple theoretical considerations, the dendritic polymers were expected to follow a logarithmic relationship between radius and molecular weight. The PAMAM dendrimers gave reasonable fits to both a power law and a logarithmic relationship from generation 0 to generation 3 (the power law gave a slightly better fit), but displayed a turnover with generation 4, which gave a smaller Stokes radius than generation 3. These results were compared with earlier results from poly (aryl ether) monodendrons, where the relationship was ambiguous between a power law and a logarithmic relationship.