Conditions Extrêmes et Matériaux : Haute Température et Irradiation

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J.B.Lena, M.Deschamps, N.F.Sciortino, G.T.Russell, S.L.Masters, 'Effects of Chain Transfer Agent and Temperature on Branching and β-Scission in Radical Polymerization of 2-Ethylhexyl Acrylate', Macromol. Chem. Physics 219 1700579 (2018) doi:10.1002/macp.201700579

Poly(2-ethylhexyl acrylate)s were synthesized by conventional radical polymerization with and without a CTA at different temperatures (from 4 °C to 140 °C). ESI-MS analyses have revealed the occurrence of β-scission and of the CTA-capped polymers at all the temperatures, as well as some termination products below from 4 °C to 65 °C. 13C melt-state NMR analyses has allowed quantification of branching and of β-scission. Both branching and β-scission are reduced when a CTA is present. The amount of β-scission increase with the synthesis temperature. The degree of branching is also more important at high temperature, but its increase is not observed anymore when the β-scission becomes important. Backbiting rates coefficient of poly(2-ethylhexyl acrylate) was evaluated from NMR results. Its frequency factor is higher than for other poly(alkyl acrylate)s but its activation energy is similar.