Two-Dimensional Spin-Diffusion NMR Reveals Differential Mixing in Biodegradable Polymer Blends

Length scales of mixing in amorphous blends of solid PCL (polycaprolactone) and PLLA (poly- l -lactic acid) were investigated as a function of preparation method. A recently described two-dimensional heteronuclear correlation (Hetcor) spin-diffusion technique (Jia et al. Macromolecules 2003, 36, 712) revealed that PCL/PLLA blends with shorter length scales of mixing, relative to solution blending, could be prepared using inclusion-compound coalescence methods (Rusa et al. Macromolecules 2000, 33, 5321). These biocompatible and biodegradable polymer blends provide a clear example of the utility of the 2D Hetcor spin-diffusion method for quantitative miscibility and phase analysis in amorphous macromolecules and their blends. The rates for intrapolymer polarization transfer vs interchain/interdomain polarization equilibration were easily differentiated using the 2D technique for either blend. As a result, spin-diffusion coefficients and miscibility length scales could be calculated by direct measurement on the blend constituents, while more traditional methods involving NMR relaxation proved inconclusive.