title: Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation.
abstract: 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.
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.|Graduate School Materials Science in Mainz , Staudingerweg 9, D-55128 Mainz, Germany.
authors.forename: Jana
authors.initials: J
authors.lastname: Herzberger
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Niederer
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.|Graduate School Materials Science in Mainz , Staudingerweg 9, D-55128 Mainz, Germany.|Max Planck Graduate Center , Staudingerweg 6, D-55128 Mainz, Germany.|Department of Dermatology, University Medical Center , Langenbeckstraße 1, D-55131 Mainz, Germany.
authors.forename: Hannah
authors.initials: H
authors.lastname: Pohlit
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Jan
authors.initials: J
authors.lastname: Seiwert
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.|Max Planck Graduate Center , Staudingerweg 6, D-55128 Mainz, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Worm
authors.affiliation: Max Planck Graduate Center , Staudingerweg 6, D-55128 Mainz, Germany.|Max Planck Institute for Polymer Research , Ackermannweg 10, D-55128 Mainz, Germany.
authors.forename: Frederik R
authors.initials: FR
authors.lastname: Wurm
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg-University Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.|Graduate School Materials Science in Mainz , Staudingerweg 9, D-55128 Mainz, Germany.
authors.forename: Holger
authors.initials: H
authors.lastname: Frey
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D005027:Ethylene Oxide / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010087:Oxides / Q000138:chemical synthesis* / Q000737:chemistry; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000480:Alkynes; D004852:Epoxy Compounds; D010087:Oxides; D011108:Polymers; D005027:Ethylene Oxide; C009068:propylene oxide