Functional PEG building blocks via copolymerization of ethylene carbonate and tert-butyl glycidyl ether

Anionic ring opening copolymerization of ethylene carbonate (EC) and tert-butyl glycidyl ether (TBGE) with CsOH as an initiator using a mono-mode microwave reactor results in poly(EO-co-TBGE) hydroxy telechelic copolymers with Mn(SEC) values between 750 and 1700 g mol−1 and dispersity indices in the range of Đ = 1.05–1.10. The reaction sequence for the formation of narrowly distributed copolymers was investigated by kinetic studies using size exclusion chromatography, 1H NMR and MALDI-ToF as analytical tools. Transcarbonylation, transalkylation and carbonate fragmentation were identified as fundamental reactions for the formation of carbonate free products with multi block microstructures. 13C NMR analysis allowed the determination of monomer sequences within the polymer chain, which confirmed its multi block type structure; different microstructures were obtained by varying the reaction time and monomer composition.