Anionic ring-opening polymerization of ethylene oxide in DMF with cyclodextrin derivatives as new initiators

• Published in: Carbohydrate polymers Vol. 94; no. 1; pp. 323 - 331
• Main Authors: Huin, Cécile, Eskandani, Zahra, Badi, Nezha, Farcas, Aurica, Bennevault-Celton, Véronique, Guégan, Philippe
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 15-04-2013; Elsevier
• Subjects: allyl alcohol; Anionic polymerization; Applied sciences; beta-Cyclodextrins - chemistry; Carbohydrate Conformation; carbon; Catalysis; Chemical Physics; Cyclodextrin; cyclodextrins; Dimethylformamide - chemistry; ethylene oxide; Ethylene Oxide - chemistry; Exact sciences and technology; Kinetics; Light; Magnetic Resonance Spectroscopy; nuclear magnetic resonance spectroscopy; Organic polymers; Physicochemistry of polymers; Physics; polyethylene glycol; Polyethylene Glycols - chemical synthesis; Polyethylene Glycols - chemistry; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Scattering, Radiation; solubility; solvents; Solvents - chemistry; Spectrometry, Mass, Electrospray Ionization; stable isotopes; Star polymers; Star polymers; Anionic polymerization; Cyclodextrin; Ring opening polymerization; Potassium Organic compounds; Priming activity; Living polymer; Experimental study; Solution polymerization; Primary alcohol; Ethylene oxide polymer; Hydroxyether; Linear polymer; Anionic catalyst; Star polymer; Comparative study; Dimethylformamide; n dimethylformamide; Radiation; Cyclodextrins; conformation; electrospray mass spectrometry; Spectrometry; macrogol derivative; Living polymerization; Light; Ethylene Oxide; Catalysis; Monofunctional initiators; Polymerization solvents; Polymers; beta cyclodextrin derivative; radiation scattering; Hydroxyl functions; chemistry; synthesis; Solvents; Magnetic Resonance Spectroscopy; Polyethylene Glycols; Anionic ring opening polymerization; Scattering; Well-defined structures; nuclear magnetic resonance spectroscopy; Polymerization; Ethylene oxide polymerizations; n; article; Mass; Cyclodextrin derivatives; beta-Cyclodextrins; Electrospray Ionization; Polyethylene oxides; solvent; Kinetics; Carbohydrate Conformation
• ISSN: 0144-8617; 1879-1344
• DOI: 10.1016/j.carbpol.2012.12.062

► Control of ethylene oxide anionic polymerization in DMF. ► New family of star polymers with a cyclodextrin core. ► DOSY NMR characterization of star polymers with various discrete number of arms.
Anionic polymerization initiated by cyclodextrins suffers from a poor solubility of those derivatives in standard polymerization solvents. The possibility to perform ethylene oxide polymerization initiated by monofunctional initiators (allyl alcohol, 2-methoxyethanol) by living ring opening polymerization in DMF, a good solvent for any CD derivative, was demonstrated by SEC, 1H and 13C NMR analyses. The study was extended to the use of native CD as initiator, leading to the synthesis of ill-defined structures, explained by the reactivity scale of the various hydroxyl functions. Two selectively modified CD derivatives are then used to synthesize a new family of star-shaped poly(ethylene oxide) polymers with CD core, having 14 or 21 arms. The polymerization was found to be living and DOSY experiments confirmed the well-defined structures for the synthesized star-polymers.