Linear Viscoelasticity and Flow of Self-Assembled Vitrimers: The Case of a Polyethylene/Dioxaborolane System

For vitrimer systems obtained by dynamic cross-linking of polymer chains, incompatibility effects between the cross-links and polymer backbone can lead to microphase separation, resulting in a network made of cross-linked aggregates. Additionally, when there is a wide distribution of the number of cross-links per chain, macrophase separation can occur, mostly due to entropic effects. Here, we investigate the linear viscoelasticity and flow of a polyethylene (PE) vitrimer that has cross-linkable dioxaborolane maleimide grafts, which self-assemble into a hierarchical nanostructure. To elucidate the role of self-assembly, we first studied dioxaborolane graft functionalized PE that was non-cross-linked. It had a terminal relaxation time that was orders of magnitude larger than both neat PE and partially peroxide cross-linked PE. When dioxaborolane cross-linker was added to form the vitrimer, the resulting material could not achieve terminal relaxation within 8 h. The soluble and insoluble portions of the PE vitrimer were then isolated and characterized. The soluble portion, which was graftpoor, expressed similar flow behavior as neat PE, while the insoluble portion-which was a graft-rich network of cross-linked aggregates-relaxed very little over 8 h. When the insoluble and soluble portions were blended, the rheological behavior of the original vitrimer was basically recovered, showing that the soluble portion acts as a lubricant. When the insoluble portion was blended with neat PE, the material relaxed much more stress but still did not reach steady-state flow within 8 h. When high stresses were applied, however, PE vitrimer flowed. Nonlinear rheology experiments revealed melt fracture at high strains and suggested that flow is enabled by rapid healing, which follows fracture events. The presence of macroscopic phase separation facilitated flow.