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Article Dans Une Revue Polymer Chemistry Année : 2019

Bromoalkyl ATRP initiator activation by inorganic salts: experiments and computations

Résumé

Ethyl α-bromophenylacetate (EBrPA) is able to initiate the bulk radical polymerisation of methyl methacrylate (MMA) under thermal conditions (90 °C) in the presence of a variety of simple alkali or alkaline-earth metal or nBu4N salts (Mt+X− with X− = chloride, bromide, iodide, carbonate, bicarbonate, sulfate, bisulfate, nitrate, hydroxide and hexafluorophosphate). Chain growth is controlled only when using iodide salts, which also gives one of the highest polymerisation rates. Using a substoichiometric amount of LiI as an activator, the polymerisation rate is unaffected by the LiI/initiator ratio when the initiator is cyanoisopropyl iodide (CPI) but increases with the activator amount when using EBrPA. Analysis of these rates in combination with the polymer molecular weights revealed a LiBr-catalysed halogen exchange between more active PMMA-I and less active PMMA-Br chains. In combination with a computational investigation by DFT methods, these findings demonstrate that while the rate of polymerisation is determined by the atom transfer equilibrium from EBrPA to the Mt+X− catalyst to yield EPA˙ and Mt+(BrX˙)−, controlled chain growth cannot be ensured exclusively by the persistent radical effect.
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Dates et versions

hal-02335256 , version 1 (30-10-2020)

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Jirong Wang, Jianyu Han, Haiyan Peng, Xiangying Tang, Jintao Zhu, et al.. Bromoalkyl ATRP initiator activation by inorganic salts: experiments and computations. Polymer Chemistry, 2019, 10 (19), pp.2376-2386. ⟨10.1039/C9PY00113A⟩. ⟨hal-02335256⟩
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