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    In Situ Synthesis of Poly(butyl methacrylate) in Anodic Aluminum Oxide Nanoreactors by Radical Polymerization: A Comparative Kinetics Analysis by Differential Scanning Calorimetry and H-1-NMR

    Year: 2021

    Journal: Polymers, Volume 13, FEB

    Authors: Leon-Boigues, Laia; Perez, Luis Andres; Mijangos, Carmen

    Organizations: Spanish Ministry of Science, Innovation and Universities (MINECO) [MAT2017-83014-C2-2-P]

    Keywords: confined polymerization; butyl methacrylate (BMA); kinetic analysis by H-1-NMR spectroscopy; polymer nanostructures

    In this work, we explore the ability to generate well-defined poly(butyl methacrylate) (PBMA) nanostructures by in situ polymerization of butyl methacrylate monomer (BMA). PBMA nanostructures of high and low aspect ratios have been successfully obtained through the free radical polymerization (FRP) of a BMA monomer in anodic aluminum oxide (AAO) nanoreactors of suitable size. A polymerization kinetics process has been followed by differential scanning calorimetry (DSC) and proton Nuclear Magnetic Resonance spectroscopy (H-1-NMR).The determination of the kinetics of polymerization through DSC is based on a quick and direct analysis of the exothermic polymerization process, whereas the analysis through H-1-NMR also allows the unambiguous chemical analysis of the resulting polymer. When compared to bulk polymerization, both techniques demonstrate confinement effects. Moreover, DSC and H-1-NMR analysis give the same kinetics results and show a gel-effect in all the cases. The number average molecular weight (Mn) of the PBMA obtained in AAO of 60-300 nm are between 30 center dot 10(3)-175 center dot 10(3) g/mol. Even if the Mn value is lower with respect to that obtained in bulk polymerization, it is high enough to maintain the polymer properties. As determined by SEM morphological characterization, once extracted from the AAO nanoreactor, the polymer nanostructures show controlled homogeneous aspect/size all throughout the length of nanopillar over a surface area of few cm(2). The Young's modulus of low aspect ratio PBMA nanopillars determined by AFM gives a value of 3.1 +/- 1.1 MPa. In this work, a 100% of PBMA polymer nanostructures are obtained from a BMA monomer in AAO templates through a quick double process: 30 min of monomer immersion at room temperature and 90 min of polymerization reaction at 60 degrees C. While the same nanostructures are obtained by polymer infiltration of PBMA at 200 degrees C in about 6 h, polymerization conditions are much softer than those corresponding to the polymer infiltration process. Furthermore, the H-1-NMR technique has been consolidated as a tool for studying the kinetics of the copolymerization reactions in confinement and the determination of monomer reactivity ratios.
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