We investigate the miscibility of a polystyrene/poly(vinyl methyl ether) (PS/PVME) blend using nuclear magnetic resonance spectroscopy. We examine 1H spin-lattice relaxation times in both the laboratory (Tin) and rotating (T~pH) frames at various temperatures. At temperatures lower than the glass transition temperature (T~) of the blend, the observed 1H relaxation time of PS is equal to that of PVME, showing that the 5/5 PS/PVME blend is miscible on a scale of 20-30 A. At temperatures much higher than T~, the observed ~H relaxation curve (T~pH) of PS apparently differs from that of PVME. They are not single exponentials. The non-exponential decays are analysed taking into account spin diffusion; the ~H spin diffusion rate between PS and PVME is found to be ~ 1000s -~ at 38°C. This spin diffusion rate is too slow for the T~pH values of PS and PVME to coincide with each other. This is attributed to the fast molecular motion of PVME. The IH relaxation curve of the phase-separated blend formed by heating above the lower critical solution temperature is markedly different from that of the homogeneous blend. On the assumption that IH spin diffusion does not occur between phase-separated domains, we analyse the ~H relaxation curve of each component polymer and obtain the stoichiometry of the phase-separated domains. We conclude that the phase separation of the 5/5 PS/PVME blend is initiated by spinodal decomposition; the phase separation rate is 0.5 min-t at 140°C.
Посилання на статтю:
13C c.p./m.a.s.n.m.r, study on the miscibility and phase separation of a polystyrene/poly(vinyl methyl ether) blend / Atsushi Asano*, K. Takegoshi* and Kunio Hikichi // Polymer. – 1994. – Vol 35. – P. 5630-5636.