Direct observation and mutual diffusion of cyclic polymers

Abstract

A cyclic polymer is one of the ideal model polymers with which to investigate the effects of chain topology on the physical properties of polymers. In this review, I summarize my recent work demonstrating that the chain structure of cyclic polymers can be directly observed by atomic force microscopy (AFM) and that the mutual diffusion of cyclic polymers is faster than that of corresponding linear ones. For direct evidence of the cyclic structure, isolated molecules of cyclic poly(sodium styrenesulfonate), which was derived from cyclic polystyrene, were observed by AFM. The mutual diffusion of cyclic polystyrene/cyclic deuterated polystyrene was investigated as a function of temperature and molecular weight by dynamic secondary ion mass spectroscopy. For the molecular weight of 113k, the mutual diffusion coefficient of cyclic polystyrene, DC, was approximately twofold larger than that of the corresponding linear polymer, DL, at all temperatures. Under an iso-free volume condition, the DC value was larger than the DL value for all the molecular weights. These results clearly show that the chain topology strongly affects the molecular motion of the whole chain. Isolated molecules of cyclic polymers were directly observed by atomic force microscopy. Interdiffusion of cyclic polystyrene/cyclic deuterated polystyrene bilayer films were investigated as functions of temperature and molecular weight by dynamic secondary ion mass spectroscopy.