Solid-State Nuclear Magnetic Resonance (NMR) and Nuclear Magnetic Relaxation Time Analyses of Molecular Mobility and Compatibility of Plasticized Polyhydroxyalkanoates (PHA) Copolymers

The molecular mobility and compatibility of plasticized polyhydroxyalkanoates (PHA) were investigated, focusing on changes due to copolymerization using either flexible poly (butylene succinate) (PBS) or rigid poly(lactic acid) (PLA) units. For the case of a poly(3-hydroxybutyrate) (PHB) unit in plasticized PHA, copolymerization of either PBS or PLA decreased (1)H and (13)C spin-lattice relaxation times in the laboratory frame (T(1)H and T(1)C) in the same manner, while PBS produced a lower (1)H spin-lattice relaxation time in the rotating frame (T(1)(ρ)H) than PLA. Both the signals of (1)H MAS (magic-angle spinning) and (13)C PST (pulse saturation transfer) MAS nuclear magnetic resonance (NMR) spectra were sharpened and increased by copolymerization with PBS. A variable temperature relaxation time analysis showed that the decrease of T(1)H values was dominated by the (1)H spin diffusion via the interface between PHB and the added polyester because of the good compatibility. Meanwhile, the decrease of T(1)C values was dominated by increasingly rapid molecular motions of PHB because of the lowered crystallinity due to the plasticization. Slow molecular motions (kHz order) were enhanced more by the addition of PBS than PLA, although rapid molecular motions (MHz order) were enhanced by either polyester. Several NMR parameters were beneficial for analyzing the manufacturing process as the indexes of polymer compatibility and molecular motions.