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Investigation of the End Group Fidelity at High Conversion during Nitroxide-Mediated Acrylate Polymerizations

Abstract : The impact of formation of midchain radicals?and more specifically the follow up reactions of ?-scission and macromonomer addition to propagating macroradicals stemming from this process?on the nitroxide-mediated polymerization of acrylates have been studied via kinetic modeling with the software package Predici on the example of butyl acrylate polymerization at 120 °C. Only small influences of the midchain radical formation on the livingness of the process is observed, however, large effects must be envisaged by the (reverse) scission reaction at high monomer-to-polymer conversions. A significant loss of livingness, depending on the temperature, monomer and initiator concentration must be expected at elevated stages of polymerizations. For a polymerization at 120 °C and a target chain length of 100, less than 75% livingness of the polymer product can be expected at 80% conversion. From this point of polymerization on, significant broadening of the overall polymer product is predicted in accordance to literature data and eventually the chain-length?conversion relation is lost at the end of reaction.
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https://hal-amu.archives-ouvertes.fr/hal-01460355
Contributor : Didier Gigmes <>
Submitted on : Tuesday, February 7, 2017 - 4:35:13 PM
Last modification on : Thursday, July 9, 2020 - 1:12:02 PM

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Yohann Guillaneuf, Didier Gigmes, Thomas Junkers. Investigation of the End Group Fidelity at High Conversion during Nitroxide-Mediated Acrylate Polymerizations. Macromolecules, American Chemical Society, 2012, 45 (13), pp.5371--5378. ⟨10.1021/ma300953b⟩. ⟨hal-01460355⟩

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