Copolymers with Tailored Microstructure as Versatile Platforms for ZIF-8 PolyMOF Growth

Abstract

In this work, we report copolymers based on zinc dimethacrylate (ZnDMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as versatile platforms for the in-situ growth of ZIF-8 polyMOFs. The copolymers were synthesized both in bulk and via surface-initiated Atom Transfer Radical Polymerization (ATRP). The composition and microstructure were investigated using the Fineman-Ross Method, complemented by characterization through X-ray photoelectron spectroscopy (XPS), proton nuclear magnetic resonance, thermogravimetric analysis, aqueous size exclusion chromatography and scanning electron microscopy. We found that differences in composition and microstructure of the resulting poly(ZnDMA-co-PEGMA)@ZIF-8 materials translated into distinct behaviors during polyMOF growth, including efficient nucleation, controlled crystalline growth, and enhanced structural stability. Overall, these results demonstrate that polyMOFs, as hybrid materials integrating metal-organic frameworks (MOFs) with polymeric precursors, constitute a versatile platform for the rational design of structured polyMOFs with potential for the development of functional materials with emergent properties.