Molecular origin of the plasticizing effect difference of glycerol with other polyols on plasticizing polyvinyl alcohol (PVA) as elucidated by solid-state NMR

Glycerol has been proved to be an effective plasticizer for polyvinyl alcohol (PVA), which can significantly increase PVA's processability and ductility, whose molecular origin remains unclear. In current study, the physical structure and chain dynamics of polyol plasticized PVA were studied in detail, including ethylene glycol, glycerol, erythritol, xylitol, and sorbitol under the same addition level. The glycerol plasticized PVA exhibits the most significant reduction in Young's modulus, enhanced superior toughness, and the lowest melting temperature (195 degrees C) as compared with other polyols. The molecular mechanism was elucidated through comprehensive analysis, with a particular focus on solid state NMR (SS NMR) results. The physical structure was first elucidated by the Small Angle X-ray Scattering (SAXS) and Wide Angle X-ray Scattering (WAXS). The crystallinity of the glycerol plasticized PVA was the lowest 29 % by WAXS and the thickness of the amorphous layer was the largest 7.76 nm by SAXS among different plasticized PVA films. This suggests the significant influence of glycerol on structure change of PVA. The molecular dynamics information was further accessed by Low Field Nuclear Magnetic Resonance (LF NMR), where two key features are obtained: i) Different dynamics dimensionality. The 1 H spin diffusion NMR was used to check the dimensionality from the aspect of chain dynamics. Compared with other plasticizers, LF NMR result shows that glycerol plasticized PVA has a two-dimensional (2D) structure; ii) Chain dynamics heterogeneity in the interphase. With respect to the chain dynamics heterogeneity in the interphase, the glycerol plasticized PVA shows the most heterogeneous dynamics, with the lowest ratio of the rigid amorphous fraction (RAF) of 0.507 in the interphase. Current study provides a versatile analytical strategy to quantify the plasticizing effect.