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Functional Polycarbonate of a d‑Glucal-Derived Bicyclic Carbonate via Organocatalytic Ring-Opening Polymerization

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journal contribution
posted on 26.06.2017, 14:49 by Alexander T. Lonnecker, Young H. Lim, Karen L. Wooley
Herein, we demonstrate the synthesis of a bicyclic carbonate monomer of a d-glucal derivative, which originated from the natural product d-glucose, in an efficient three-step procedure and its ring-opening polymerization (ROP), initiated by 4-methylbenzyl alcohol, via organocatalysis. The ROP behavior was studied as a function of time, catalyst type, and catalyst concentration by using size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Using a cocatalyst system of 1,8-diazabicyclo[5.4.0]­undec-7-ene and 1-(3,5-bis­(trifluoromethyl)­phenyl)-3-cyclohexyl-2-thiourea (5 mol %) afforded poly­(d-glucal-carbonate) (PGCC) with almost complete monomer conversion (ca. 99%) within 1 min, as analyzed by 1H NMR spectroscopy, and a monomodal SEC trace with dispersity of 1.13. The resulting PGCCs exhibited amorphous characteristics with a relatively high glass transition temperature at ca. 69 °C and onset decomposition temperature at ca. 190 °C, as analyzed by differential scanning calorimetry and thermogravimetric analysis, respectively. This new type of potentially degradable polymer system represents a reactive functional polymer architecture.