Chemistry Publications

Document Type

Article

Publication Date

7-16-2018

Journal

Macromolecules

Volume

51

Issue

15

First Page

5501

Last Page

5510

URL with Digital Object Identifier

https://doi.org/10.1021/acs.macromol.8b01007

Abstract

The synthesis of poly(ethyl glyoxylate)s (PEtGs) by anionic polymerization was explored. PEtGs are a subclass of stimuli-responsive self-immolative polymers with promising properties for applications as coatings, sensors, and drug delivery vehicles. In this report, a new purification procedure for the preparation of highly pure ethyl glyoxylate (EtG), suitable for anionic polymerization reactions, and the first successful examples of controlled polymerization of EtG are described. n-BuLi, PhLi, and t-BuLi were employed as initiators under different experimental conditions and their behavior was examined using NMR spectroscopy, size exclusion chromatography, and thermal analysis to develop an optimized procedure. As functional alkoxide initiators, propargyl alkoxide was employed in optimization studies and poly(ethylene glycol) (PEG) dialkoxide was utilized for the direct synthesis of PEtG-PEG-PEtG copolymers. The new polymerization method revealed many features of controlled polymerization reactions, yielding PEtGs with predictable molar masses and relatively low dispersity values.

Notes

“This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.8b01007"

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