Melts of ultrahigh molecular weight polyethylene (UHMWPE) entangled significantly, suffering processing difficulty. In this work, we prepared partially disentangled UHMWPE by freeze-extracting, exploring the corresponding enchantment of chain mobility. Fully refocused 1H free induction decay (FID) was used to capture the difference in chain segmental mobility during the melting of UHMWPE with different degrees of entanglement by low-field solid-state NMR. The longer the polyethylene (PE) chain is in a less-entangled state, the harder the process of merging into mobile parts after detaching from crystalline lamella during melting. 1H double quantum (DQ) NMR was further used to obtain information caused by residual dipolar interaction. Before melting, the DQ peak appeared earlier in intramolecular-nucleated PE than in intermolecular-nucleated PE because of the strong constraints of crystals in the former one. During melting, less-entangled UHMWPE could keep disentangled while less-entangled high density polyethylene (HDPE) could not. Unfortunately, no noticeable difference was found in DQ experiments between PE melts with different degrees of entanglement after melting. It was ascribed to the small contribution of entanglements compared with total residual dipolar interaction in melts. Overall, less-entangled UHMWPE could reserve its disentangled state around the melting point long enough to achieve a better way of processing.
Keywords: UHMWPE; crystallization; entanglement; relaxation; solid-state NMR.