Bromoalkyl ATRP initiator activation by inorganic salts: experiments and computations - Archive ouverte HAL Accéder directement au contenu
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.
Fichier principal
Vignette du fichier
Polym. Chem., 2019, 10, 2376.pdf (328.21 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

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

Identifiants

Citer

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⟩
54 Consultations
186 Téléchargements

Altmetric

Partager

Gmail Mastodon Facebook X LinkedIn More