A solvent-free route of initiated chemical vapor deposition (iCVD) was used to synthesize a bio-renewable poly(α-Methylene-γ-butyrolactone) (PMBL) polymer. α-MBL, also known as tulipalin A, is a bio-based monomer that can be a sustainable alternative to produce polymer coatings with interesting material properties. The produced polymers were deposited as thin films on three different types of substrates-polycarbonate (PC) sheets, microscopic glass, and silicon wafers-and characterized via an array of characterization techniques, including Fourier-transform infrared (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), ultraviolet visible spectroscopy (UV-vis), differential scanning calorimetry (DSC), size-exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Optically transparent thin films and coatings of PMBL were found to have high thermal stability up to 310 °C. The resulting PMBL films also displayed good optical characteristics, and a high glass transition temperature (Tg~164 °C), higher than the Tg of its structurally resembling fossil-based linear analogue-poly(methyl methacrylate). The effect of monomer partial pressure to monomer saturation vapor pressure (Pm/Psat) on the deposition rate was investigated in this study. Both the deposition rate and molar masses increased linearly with Pm/Psat following the normal iCVD mechanism and kinetics that have been reported in literature.
Keywords: Butyrolactones; Sustainability; bio-based; iCVD; polymer coatings; thermal stability.