Plasticization of a Semicrystalline Metallosupramolecular Polymer Network.

Abstract

The assembly of ligand-functionalized (macro)monomers with suitable metal ions affords metallosupramolecular polymers (MSPs). On account of the reversible and dynamic nature of the metal-ligand complexes, these materials can be temporarily (dis-)assembled upon exposure to a suitable stimulus, and this effect can be exploited to heal damaged samples, to facilitate processing and recycling, or to enable reversible adhesion. We here report on the plasticization of a semicrystalline, stimuli-responsive MSP network that was assembled by combining a low-molecular-weight building block carrying three 2,6-bis(1'-methylbenzimidazolyl) pyridine (Mebip) ligands and zinc bis(trifluoromethylsulfonyl)imide (Zn(NTf2)2). The pristine material exhibits high melting (T m = 230 °C) and glass transition (T g ≈ 157 °C) temperatures and offers robust mechanical properties between these temperatures. We show that this regime can be substantially extended through plasticization. To achieve this, the MSP network was blended with diisodecyl phthalate. The weight fraction of this plasticizer was systematically varied, and the thermal and mechanical properties of the resulting materials were investigated. We show that the T g can be lowered by more than 60 °C and the toughness above the T g is considerably increased.