Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers

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• 作者：Benedikt S. Soller ; Stephan Salzinger ; Bernhard Rieger
• 刊名：Chemical Reviews
• 出版年：2016
• 出版时间：February 24, 2016
• 年：2016
• 卷：116
• 期：4
• 页码：1993-2022
• 全文大小：1741K
• 年卷期：
  Benedikt S. Soller received his B.Sc. (2010) and his M.Sc. degree (2013) in chemistry from the Technische Universität München under the guidance of Prof. Bernhard Rieger. In 2011, he carried out research on emulsion polymerization at BASF SE in Ludwigshafen. During his master’s studies, he spent two months at King Abdullah University of Science and Technology in Saudi Arabia as part of a research stay and six months at Ateneo de Manila University in the Philippines. He is currently a Ph.D. candidate with the group of Prof. Rieger. His research interests include the polymerization of vinylic monomers, further development of REM-GTP catalysts, stereoregular polymerization, and the application of SI-GTP on SiNCs for the preparation of hybrid materials. Besides his academic research interests, he is improving his knowledge of the Korean language and photography.
  Stephan Salzinger studied chemistry at the Technische Universität München and received his M.Sc. in 2010. In 2009, he carried out research on self-assembling peptide nanotubes under the guidance of M. Amorín and J. R. Granja at the Universidad de Santiago de Compostela. In his master’s thesis in the group of Bernhard Rieger, he investigated the stereoregularity and thermoresponsive behavior of vinylphosphonates. His Ph.D. work was focused on the extension of REM-GTP to new monomer classes and the elucidation of the mechanism of vinylphosphonate REM-GTP, for which he received a scholarship from the Fonds der Chemischen Industrie. After graduating in 2013, he joined the Advanced Materials & Systems Research laboratories of BASF SE in Ludwigshafen as a research engineer in polymer process development.
  Bernhard Rieger studied chemistry at the Ludwig-Maximilians-Universität München (LMU) and received his Ph.D. in 1988. After research at the University of Massachusetts at Amherst and in the plastics laboratory of BASF SE, he received his habilitation in 1995 at the University of Tübingen. In 1996, he became professor at the Department Materials and Catalysis at the University of Ulm. Since 2006, he has been professor at the Technische Universität München at the WACKER-Chair of Macromolecular Chemistry and director of the Institute of Silicon Chemistry. He is a fellow of the National Academy of Science and Engineering “acatech” (2013), a member of the European Academy of Science (2011), a member of the Finnish Academy of Science and Letters (2008), and an Honorary Doctor Dr. h.c. phil. of the University of Helsinki (2007). In 2013, he was awarded the Wöhler Prize for Sustainable Chemistry and holds a Philip Morris Award.
• ISSN：1520-6890

文摘

This review focuses on introducing and explaining the rare earth metal-mediated group transfer polymerization (REM-GTP) of polar monomers and is composed of three main sections: poly(vinylphosphonate)s, surface-initiated group transfer polymerization (SI-GTP), and extension to N-coordinating Michael-type monomers (2-vinylpridine (2VP), 2-isopropenyl-2-oxazoline (IPOx)). The poly(vinylphosphonate)s section is divided into two parts: radical, anionic, and silyl ketene acetal group transfer polymerization (SKA-GTP) of vinylphosphonates in comparison to REM-GTP, and properties of poly(vinylphosphonate)s. The mechanism of vinylphosphonate REM-GTP is discussed in detail for initiation and propagation including activation enthalpies ΔH^‡ and entropies ΔS^‡ according to the Eyring equation. SI-GTP is presented as a method for surface functionalization, and recent trends for 2VP and IPOx polymerization are summarized. This review will serve as a good resource or guideline for researchers who are currently working in the field of rare earth metal mediated polymerization catalysis as well as for those who are interested in beginning to employ rare earth metal complexes for the synthesis of new materials from polar monomers.