Controlled/living polymerization of methyl methacrylate using new sterically hindered imidazoline nitroxides prepared via intramolecular 1,3‐dipolar cycloaddition reaction |
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| Authors: | Mariya V Edeleva Dmitriy A Parkhomenko Denis A Morozov Sergey A Dobrynin Dmitry G Trofimov Beket Kanagatov Igor A Kirilyuk Elena G Bagryanskaya |
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| Institution: | 1. International Tomography Center SB RAS, , Novosibirsk, 630090 Russia;2. Novosibirsk State University, , Novosibirsk, 630090 Russia;3. N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, , Novosibirsk, 630090 Russia |
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| Abstract: | A series of imidazoline nitroxides with bulky spirocyclic moieties at the positions 2 or 5 of imidazole ring were synthesized using intramolecular 1,3‐dipolar cycloaddition in 2H‐imidazole 1‐oxides or 4H‐imidazole 3‐oxides with pent‐4‐enyl groups followed by isoxazolidine ring opening and oxidation. Capability of the nitroxides to control radical polymerization of methyl methacrylate (MMA) and styrene was investigated. For that purpose, alkoxyamines were synthesized from the aforementioned nitroxides and tert‐butyl α‐bromoisobutyrate. Homolysis rate constants of the alkoxyamines were measured and possible contributions of side reactions were quantified. Nitroxide‐mediated polymerization of styrene and MMA was studied using the alkoxyamines as initiators. MMA polymerization was found to proceed in controlled regime up to 55% of monomer conversion and the polymer obtained was able to reinitiate the polymerization of styrene. Quota of “living” chains estimated to reach 90%. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 929–943 |
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| Keywords: | block copolymers kinetics (polym ) living radical polymerization (LRP) methyl methacrylate NMR |
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