Structurally Enhanced Self-Plasticization of Poly(vinyl chloride) via Click Grafting of Hyperbranched Polyglycerol

A highly self-plasticized poly(vinyl chloride) (PVC) is demonstrated for the first time via click grafting of hyperbranched polyglycerol (HPG). The plasticizing effect of the grafted HPG on PVC is systematically investigated by various analytical methods. The amorphous and bulky dendritic structure of HPG efficiently increases the free volume of the grafted PVC, which leads to a remarkably lower glass transition temperature comparable to that of the conventional plasticized PVC. Viscoelastic analysis reveals that HPG considerably improves the softness of the grafted PVC at room temperature and promotes the segmental motion in the system. The HPG-grafted PVC films exhibit an exceptional stretchability unlike the mixture of PVC and HPG because the covalent attachment of HPG to PVC allows it to maintain its homogeneous and well-organized architecture under tensile stretching. The work provides valuable insights into the design of highly flexible and stretchable polymeric materials by means of introducing hyperbranched side chains.