Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis,characterization, and DFT study |
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Authors: | Abolfazl Heydari Maryam Hosseini Mahdieh Darroudi Masoumeh Behzadi Viktor Hronský Gabriel Sučik Hossein Rouh Hassan Sheibani |
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Institution: | 1. Polymer Institute of the Slovak Academy of Sciences, Slovakia;2. Faculty of Physics, Shahid Bahonar University of Kerman, Kerman, Iran;3. Department of Medical Biotechnology and Nanotechnology, School of Science, Mashhad University of Medical Science, Mashhad, Iran;4. Laboratoire de Chimie et Systémique Organométalliques, Institut de Chimie de Strasbourg (UMR 7177) CNRS/Université de Strasbourg, Strasbourg, France
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran;5. Department of Physics, Technical University of Košice, Košice, Slovakia;6. Faculty of Materials, Metallurgy and Recycling, Technical University of Košice, Košice, Slovakia;7. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas, USA;8. Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran |
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Abstract: | In this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene-co-p-chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene-co-styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT-IR, high-resolution solid-state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap. |
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Keywords: | ketene polystyrene Meldrum's acid mechanism density functional theory |
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