Polymerization of ethylene oxide, propylene oxide, and other alkylene oxides: Synthesis, novel polymer architectures, and bioconjugation

Jana Herzberger, Kerstin Niederer, Hannah Pohlit, Jan Seiwert, Matthias Worm, Frederik R. Wurm, Holger Frey*

*Corresponding author for this work

Research output: Contribution to journalReview articleAcademicpeer-review

297 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)2170-2243
Number of pages74
JournalChemical reviews
Volume116
Issue number4
DOIs
Publication statusPublished - 24 Feb 2016
Externally publishedYes

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