TY - DATA T1 - Anionic Ring-Opening Polymerization of Hexafluoropropylene Oxide Using Alkali Metal Fluorides as Catalysts: A Mechanistic Study PY - 2009/02/10 AU - Sergei V. Kostjuk AU - Esteban Ortega AU - François Ganachaud AU - Bruno Améduri AU - Bernard Boutevin UR - https://acs.figshare.com/articles/journal_contribution/Anionic_Ring_Opening_Polymerization_of_Hexafluoropropylene_Oxide_Using_Alkali_Metal_Fluorides_as_Catalysts_A_Mechanistic_Study/2879584 DO - 10.1021/ma8012338.s001 L4 - https://ndownloader.figshare.com/files/4577458 KW - molar mass polymers KW - hexafluoropropylene oxide KW - fluoride KW - 1 H NMR KW - Alkali Metal Fluorides KW - polymerization KW - KF KW - batch KW - monoadduct CF 3CF KW - masse KW - DPn KW - 4F N2 - The anionic ring-opening polymerization of hexafluoropropylene oxide using the conventional alkali metal fluorides/tetraglyme catalytic system in the presence of different fluorinated solvents at various temperatures and under batch conditions is reported. Basically, the sodium fluoride (NaF)/tetraglyme system gave only monoadduct CF3CF2CO2CH3, while cesium fluoride (CsF)/tetraglyme produced oligomeric product with number-average degree of polymerization (DPn) less than 5. The higher molar mass polymers were synthesized using the potassium fluoride (KF)/tetraglyme catalytic system and 1,1,1,3,3-pentafluorobutane (C4F5H5) or 1,3-bis(trifluoromethyl)benzene as solvent at 0 °C. Under these conditions, polymers with number-average molar masses ranging between 2500 and 3500 g mol−1 were obtained in high contents (>90%) and almost without any low molar mass (DPn ≤ 5) contaminants (4−7%). Polymers which chain ends were derived into methyl esters were fully characterized by gas chromatography, 19F and 1H NMR, and MALDI-TOF-MS spectroscopy. A kinetic study allowed us to propose a tentative mechanism entailing (i) the livingness of the polymerization of the hexafluoropropylene oxide with KF/tetraglyme catalytic system and (ii) the importance on the control of molar masses of the biphasic gas/liquid environment in the batch autoclave. ER -