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Issue 22, 2013
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SET-LRP of methacrylates in fluorinated alcohols

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Abstract

Activated Cu(0) wire-mediated single-electron transfer living radical polymerization (SET-LRP) of methyl methacrylate (MMA), ethyl methacrylate (EMA) and n-butyl methacrylate (BMA) was performed in two fluorinated alcohols, 2,2,2-trifluoroethanol (TFE) and 2,2,3,3-tetrafluoropropanol (TFP) using tosyl chloride (TsCl) as initiator, hydrazine-activated Cu(0) wire as catalyst, and Me6-TREN as ligand at 50 °C. The ability of these two solvents to solubilize these monomers, the resulting polymers, and mediate an efficient disproportionation of Cu(I)Br in the presence of Me6-TREN ligand to produce the “nascent” Cu(0) activator, Cu(II)Br2 deactivator and to stabilize Cu(II)Br2/Me6-TREN complex make them excellent solvents for SET-LRP of methacrylates. To the best of our knowledge, this is the first report of SET-LRP of methacrylates in fluorinated alcohols and also the first efficient SET-LRP of EMA and BMA in any solvent. The kinetic experiments and molecular weight analyses demonstrate that in all experiments a living polymerization takes place with excellent evolution of molecular weight and with narrow molecular weight distribution until almost complete monomer conversion. It was also demonstrated that the rate of polymerization conducted in TFE and TFP could be significantly enhanced by a synergistic solvent effect upon addition of a small amount of water, which mediates an even faster disproportionation of Cu(I)Br into Cu(0) activator and Cu(II)Br2 deactivator.

Graphical abstract: SET-LRP of methacrylates in fluorinated alcohols

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Article information


Submitted
09 Jul 2013
Accepted
19 Jul 2013
First published
19 Jul 2013

Polym. Chem., 2013,4, 5563-5569
Article type
Paper

SET-LRP of methacrylates in fluorinated alcohols

S. R. Samanta, A. Anastasaki, C. Waldron, D. M. Haddleton and V. Percec, Polym. Chem., 2013, 4, 5563
DOI: 10.1039/C3PY00902E

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