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MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization

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Abstract

The p(MMA-b-t-BuA) copolymer was prepared using the initiation system methyl 2-lithioisobutyrate/lithium/tert-butoxide (MIB-Li/t-BuOLi). A low-molecular-weight fraction was isolated and analyzed by MALDI-TOF mass spectrometry with the aim to find out structures of products of self-termination, which proceeds mainly after the addition of t-BuA into the living PMMA. The main self-termination products are formed after addition of one or two t-BuA units onto living PMMA-Li by backbiting reaction of t-BuA-Li chain-ends and carbonyl group of the antepenultimate MMA units of the same chain. The oxoesters generated in this way contain hydroxygroup, and its hydrogen can protonize any of the living chains, regardless of the type of its terminal unit. Signals of the chains, terminated by this protonization, have also been found in the spectra. Thus, the first direct evidences for the structures of the self-termination products in the anionic methacrylate/acrylate block copolymerization were obtained in this way.

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Acknowledgments

Financial support from the Academy of Sciences of the Czech Republic (Project AVOZ 4050913) is highly appreciated.

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Authors and Affiliations

  1. Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 16206, Prague, Czech Republic

    Petr Vlček, Eva Čadová, Jiří Horský & Miroslav Janata

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  1. Petr Vlček
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  2. Eva Čadová
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Correspondence to Petr Vlček.

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Vlček, P., Čadová, E., Horský, J. et al. MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization. Polym. Bull. 72, 2227–2239 (2015). https://doi.org/10.1007/s00289-015-1400-x

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  • DOI: https://doi.org/10.1007/s00289-015-1400-x

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