Glycidyl Tosylate: Polymerization of a "Non‐Polymerizable" Monomer permits Universal Post‐Functionalization of Polyethers. Issue 37 (19th August 2019)

• Record Type: Journal Article
• Authors: Jung, Philipp; Ziegler, Arthur D.; Blankenburg, Jan; Frey, Holger
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 37(2019)
• Page Start: 12883
• Page End: 12886
• Publication Date: 2019-08-19
• Subjects: functionalization -- poly(ethylene oxide) -- poly(propylene oxide) -- polyether -- ring-opening polymerization; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201904203
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Glycidyl tosylate appears to be a non‐polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer‐activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7–25 % incorporated tosylate‐moieties. The microstructure of the copolymers was investigated via in situ 1 H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate‐moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization. Abstract : A monomer‐activated mechanism allows the non‐polymerizable monomer glycidyl tosylate to be copolymerized with ethylene oxide (EO) and propylene oxide (PO), yielding copolymers with 7–25 % incorporated tosylate‐moieties.