Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

详细信息    查看全文

• 作者：Jana Herzberger ; Kerstin Niederer ; Hannah Pohlit ; Jan Seiwert ; Matthias Worm ; Frederik R. Wurm ; Holger Frey
• 刊名：Chemical Reviews
• 出版年：2016
• 出版时间：February 24, 2016
• 年：2016
• 卷：116
• 期：4
• 页码：2170-2243
• 全文大小：4712K
• 年卷期：
  Jana Herzberger (first from the left) studied Chemistry at the Johannes Gutenberg-University Mainz (JGU), spending an exchange semester at the Polymer Science and Engineering Department, UMass-Amherst. She is currently working on her Ph.D. thesis, funded by the Fonds der Chemischen Industrie and the Excellence Initiative, “Materials Science in Mainz” (DFG/GSC 266). Her research focuses on the synthesis of multi-functional polyethylene glycols from novel epoxide building blocks.
  Kerstin Niederer (second from the left) studied Biomedical Chemistry at the JGU Mainz, where she received her diploma degree in 2013. Currently, she is working on her Ph.D. thesis at the University of Mainz and the Seoul National University (South Korea) as a fellow of the “International Research Training Group 1404”. Her research interests focus on multifunctional linear and hyperbranched polyethers.
  Hannah Pohlit (third from the left) studied Biomedical Chemistry at the JGU Mainz. Since 2012, she has been a Ph.D. student both in the research laboratories of Prof. Dr. Holger Frey at the Institute of Organic Chemistry and in the lab of Prof. Dr. Joachim Saloga at the Department of Dermatology in Mainz, focusing on encapsulation of allergens into degradable PEG-nanoparticles. Her research is supported by the Graduate School MAINZ, the Max Planck Graduate Center (MPGC), and the Gutenberg-Akademie.
  Jan Seiwert (middle) studied chemistry at the JGU Mainz and is a Ph.D. student in the group of Prof. Holger Frey. His research interests are focused on the synthesis, characterization and application of novel hyperbranched poly(alkylene oxide)s obtained from the copolymerization of glycidol with EO, PO, and BO.
  Matthias Worm (third from the right) studied Chemistry at the JGU Mainz and at the Seoul National University in South Korea. Since 2013 he is a Ph.D. student in the research group of Prof. Holger Frey focusing on the synthesis of cleavable polyether-based structures. His research is funded by the Max Planck Graduate Center and the Sonderforschungsbereich SFB 1066.
  Dr. Frederik R. Wurm (born 1981; second from the right) studied Chemistry at the JGU Mainz (D) and received his PhD in 2009 under guidance of Holger Frey. After two year stay at EPFL (CH) as a Humboldt fellow, he joined the department of Katharina Landfester at MPIP and was selected as Junior Faculty Member of the Max Planck Graduate Center. In his interdisciplinary research poly(ether)s and poly(phosphoester)s are the major synthetic platforms to prepare novel materials for adhesives, tissue engineering, sensing, nanocarriers, and polymer therapeutics.
  Prof. Holger Frey (born 1965; first from the right) became chaired professor for Organic and Macromolecular Chemistry at the JGU Mainz in 2003 after his studies at the University of Freiburg, Carnegie-Mellon University Pittsburgh (U.S.A.), and Ph.D. thesis at the University of Twente (NL). His research interests are centered in the areas of oxyanionic and carbanionic polymerization, polyester synthesis and hyperbranched polymers. The work of his group at JGU generally aims at the development of convenient routes for the preparation of polymers with special architecture, functionality, and materials properties. He has authored more than 300 peer-reviewed original works and reviews in this area.
• ISSN：1520-6890

文摘

The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a “polyether universe” may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.