The phase-separated structure and molecular mobility for core-shell type polymer particles composed of poly(butyl acrylate) (PBA) and poly(methyl methacrylate) (PMMA) have been examined by high-resolution solid-state 13 C n.m.r. spectroscopy. These types of polymer particles were prepared by the two-step emulsion polymerization of BA and MMA in the presence or absence of ally methacrylate (AMA) as a crosslinking agent. The analysis of the 1 H– 13C cross polarization process has revealed that molecular mobility of the main-chain of PBA is significantly restricted for sample BA2M prepared in the presence of 1.6 wt% AMA. 1 H spin–lattice relaxation time measurements in the rotating frame have also revealed that the PBA and PMMA phases are phase-separated in a scale of several nm for the polymer particles. Furthermore, the 1 H spin diffusion process, measured by the combined pulse sequence of the Goldman–Shen pulse sequence and the CP process, has been successfully analyzed in terms of the equation derived by the simple two-spin cross relaxation theory. The time constant TSD for the 1 H spin diffusion between two polymers obtained through this analysis has been found to be a useful parameter to elucidate the phase-separated structure. On the basis of these results, it is concluded that the PBA/PMMA polymer particles have a rather incompletely phase-separated core-shell type structure but the addition of an appropriate amount of AMA improves such a structure by confining the distribution of PMMA domains around the surface of the polymer particles probably as a result of the preferential crosslinking in the PBA phase.
Посилання на статтю:
Structural analysis of core-shell type polymer particles composed of poly(butyl acrylate) and poly(methyl methacrylate) by high-resolution solid-state 13C n.m.r. spectroscopy / Masato Ishida, Junji Oshima, Kunio Yoshinaga, Fumitaka Horii // Polymer. – 1999. – N 40. – P. 3323–3329.
