Probing the Properties of New Fluorocyclic‐Polyhedral Oligomeric Silsesquioxane Polymers via a Model Compound

ABSTRACT Two new fluorocyclic‐polyhedral oligomeric silsesquioxane (POSS) monomers are synthesized using the selective nucleophilic addition of thiols to perfluorocyclopentene. These monomers differ only in the chain length attached to the fluorocyclic unit. Additionally, a fluorocyclic monomer without POSS is synthesized and used as a control. The monomers undergo full characterization before being homopolymerized and copolymerized with methyl methacrylate through free radical polymerization techniques. Characterization of the resulting polymers is performed using 1 H and 19 F NMR spectroscopy and gel permeation chromatography. Spectroscopic analysis confirms the successful incorporation of the fluorocyclic monomers into the polymer structures. Molecular weight and dispersity values align with the expected polymerization method. Differential scanning calorimetry and thermogravimetric analysis reveal that slight variations in chain length, the presence of the fluorocyclic unit, and incorporation of the POSS cage significantly influence the thermal properties, which are discussed herein.