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Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange
Author(s) -
De Bon Francesco,
Isse Abdirisak A.,
Gennaro Armando
Publication year - 2019
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201900192
Subject(s) - atom transfer radical polymerization , polymer chemistry , methyl methacrylate , catalysis , chemistry , polymerization , polymer , solvent , radical polymerization , halogen , chain transfer , methacrylate , living free radical polymerization , trifluoromethanesulfonate , organic chemistry , alkyl
Abstract Electrochemically mediated atom transfer radical polymerization ( e ATRP) of methyl methacrylate (MMA) was studied in 1‐butyl‐3‐methylimidazolium triflate ([BMIm][OTf]) and ethanol. When 2‐bromopropionitrile and ethyl 2‐bromoisobutyrate were used as initiators, poorly controlled or uncontrolled polymerizations yielding polymers with molecular weights largely exceeding the theoretical values were obtained. Poor control was attributed to a reactivity mismatch between initiator and dormant species, which was successfully suppressed by combining e ATRP with catalytic halogen exchange. Well‐defined polymers ( M n >30000 and Ð <1.2) were obtained in both solvents under optimized conditions. The possibility of using PMDETA as an inexpensive ligand in combination with ethyl α‐bromophenylacetate as initiator was also successful. Good chain‐end fidelity during e ATRP was confirmed by chain extension of PMMA‐Cl macroinitiator with MMA in ethanol. Polymers prepared in both solvents were found to be mainly syndiotactic, without any solvent effect on tacticity.