Abstract
To elucidate the effects of hydrogen bonds between polymer chains and small molecules on the mobility of small molecules, the mobilities of TEMPO (SPIV), TEMPOL containing a hydroxyl group (SPV), and TEMPONE containing a carbonyl group (SPVI) were investigated by means of electron spin resonance (ESR) measurements, and compared with the mobility of TEMPAMINE containing amino group (SPIII) examined previously. T50G, at which the extrema separation of ESR spectra becomes 5 mT (50 G) decreased in the order of SPVI>SPIII>SPV>SPIV, suggesting that the functional groups of the spin probes strongly affect the mobilities of the spin probes. For all the spin probes, T50G decreased with an increase in the methylene chain length of the nylon. However, the effects of drawing on the mobility were found only for SPIII. In the Arrhenius plots of rotational correlation times, one or two crossover points were defined. The crossover point at the lower temperature, Tn′, is considered to be the temperature at which the full rotation of a piperidine ring in the spin probes occurs, and that at the higher temperature, Tn, is presumed to be the temperature at which the rotational motion of the whole probe molecule becomes coupled with translational diffusion. For SPVI only, could Tn′ not be observed. The variation of the rotational behavior in the spin probes is due to the way in which hydrogen bonds form between their functional groups and the nylon chains. Such a variation was also found in the activation energies for rotation. The activation energy for rotation in the temperature region between Tn′ and Tn was greatly dependent on the structure of the spin probe.
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Hamada, K., Iijima, T. & McGregor, R. Effects of Hydrogen Bonds on the Mobility of Spin Probes in Nylon Films. Polym J 19, 709–717 (1987). https://doi.org/10.1295/polymj.19.709
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DOI: https://doi.org/10.1295/polymj.19.709