Abstract
In recent years the concept of two-dimensional exchange NMR spectroscopy, which is well-established as a tool for structural elucidation of biopolymers in solution, has successfully been applied to solid synthetic polymers. This review introduces the methodology of 2D exchange NMR in solids and illustrates its power by a number of experimental examples. Structural aspects include the packing of amorphous and frozen liquid-crystalline polymers as well as domain sizes in polymer blends. The unique information about slow molecular dynamics provided by 2D exchange NMR is demonstrated for the chain motion of polypropylene in both its crystalline and amorphous modifications. It is shown that 2D exchange NMR is also able to detect chain diffusion between crystalline and amorphous regions. As an example of new polymeric materials, the rotational motion of the discotic units in hairy rod macromolecules is presented. It is shown that the side-group motion in glassy poly(methyl methacrylate) is a rather complex process involving a coupling to a rocking motion of the main chain. Finally it is demonstrated that 2D exchange NMR can also be applied to determine the orientational distribution function in partially ordered polymers. Here a biaxially stretched film of poly(ethylene terephthalate) provides an illustrative example.
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