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Issue 17, 2018
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SET-LRP in biphasic mixtures of fluorinated alcohols with water

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Biphasic-binary mixtures of 2,2,2-trifluoroethanol (TFE) or 2,2,3,3-tetrafluoropropanol (TFP) with water were used as reaction media to synthesize well-defined poly(methyl acrylate) (PMA) with chain end functionality close to 100% by SET-LRP. Non-activated Cu(0) wire was used as a catalyst, taking advantage of the Cu(0)-activation property that these fluorinated alcohols possess. Biphasic-binary mixtures of water, containing a ligand and Cu(II)Br2 either generated by disproportionation of Cu(I)Br or externally added, and an organic solvent, containing a monomer and a polymer, were studied. Two N-ligands were investigated: the classic tris(2-dimethylaminoethyl)amine (Me6-TREN) and tris(2-aminoethyl)amine (TREN), as a more economically attractive alternative for technological purposes. The results reported here support the replacement of Me6-TREN by TREN, taking into account the fact that the latter requires small loadings of an externally added Cu(II)Br2 deactivator and a ligand in the water phase to mediate a living radical polymerization process. Both catalytic systems ensure efficient SET-LRP processes with first order kinetics to high conversion, linear dependence of experimental Mn on conversion, narrow molecular weight distribution, and near-quantitative chain end functionality.

Graphical abstract: SET-LRP in biphasic mixtures of fluorinated alcohols with water

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Publication details

The article was received on 13 Jan 2018, accepted on 16 Mar 2018 and first published on 20 Mar 2018

Article type: Paper
DOI: 10.1039/C8PY00062J
Citation: Polym. Chem., 2018,9, 2313-2327

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    SET-LRP in biphasic mixtures of fluorinated alcohols with water

    A. Moreno, T. Liu, L. Ding, I. Buzzacchera, M. Galià, M. Möller, C. J. Wilson, G. Lligadas and V. Percec, Polym. Chem., 2018, 9, 2313
    DOI: 10.1039/C8PY00062J

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