Polymer-grafted metal-organic frameworks (MOFs) can combine the properties of MOFs and polymers into a single, matrix-free composite material. Herein, we examine polymer-grafted MOF particles (using UiO-66 as a model system) to examine how the molecular weight, grafting density, and chemical functionality of the polymer graft affects the preparation of free-standing self-assembled MOF monolayers (SAMMs). The physical properties of the monolayers are influenced by the choice of polymer, and robust, flexible monolayers were achieved more readily with poly(methyl acrylate) when compared to poly(methyl methacrylate) or poly(benzyl methacrylate). Molecular dynamics simulations were carried out to provide insights into the orientation and ordering of MOFs in the monolayers with respect to MOF size, graft length, and hydrophobicity. The relationship between molecular weight and graft density of the polymer brush was investigated and related to polymer brush conformation, offering design rules for further optimizations to balance mechanical strength, MOF weight fraction, and processability for this class of hybrid materials.
Keywords: coarse-grained model; metal−organic frameworks; molecular dynamics simulations; polymer brushes; polymers; self-assembly.