Protective features, durability and biodegration study of acrylic and methacrylic fluorinated polymer coatings for marble protection

In the present paper, a new fluorine based methacrylic monomer, 1H,1H,2H,2H-Perfluoro-octyl-methacrylate (POMA), was synthesized via esterification reaction from methacryloyl chloride and 1H,1H,2H,2H-Perfluoro-1-octanol. Furthermore, POMA was used to prepare with methyl methacrylate (MMA) via free radical polymerization a novel fluorinated methacrylic polymer (MMA_POMA), in order to overcome the well-known technical problems related to the use of acrylic monomer-based commercial protectives, such as Paraloid B72®. Indeed, in Paraloid B72® −obtainable from the copolymerization reaction of ethyl methacrylate (EMA) and methyl acrylate (MA)- the presence of an acrylic hydrogen atom in alpha to the carbonyl group can start photo-chemical degradation reactions that are able to promote fungi attack and proliferation. The properties of MMA_POMA and the two references synthesized, EMA_MA and EMA_MA_POMA −in terms of macromolecular structure, molecular weights, thermal features and water repellency- were determined; furthermore, the long-term behavior of these polymeric protective agents was estimated by means of accelerated aging tests exploiting UV radiations. Their behavior over time was checked via Size Exclusion Chromatography (SEC), Fourier Transform Infrared (FT-IR) spectroscopy and biodegradation assay. Lastly, MMA_POMA resin was applied on two marble substrates −Calcite and Dolomite- and its wetting properties were successfully assessed and compared to the same features displayed by the reference polymers. This work demonstrates that a polymer protective prepared starting from methacrylic and fluorinated monomers, i.e. MMA and POMA, is an efficient way to obtain resins with satisfactory water repellent properties and enhanced durability than acrylic based polymers without the use of any photo stabilizer additive.