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Two-compartment kinetic Monte Carlo modelling of electrochemically mediated ATRP†
Reaction Chemistry & Engineering ( IF 3.9 ) Pub Date : 2018-09-25 00:00:00 , DOI: 10.1039/c8re00156a
Dagmar R. D'hooge 1, 2, 3, 4, 5 , Marco Fantin 1, 2, 3, 4, 5 , Andrew J. D. Magenau 1, 2, 3, 4, 5 , Dominik Konkolewicz 1, 2, 3, 4, 5 , Krzysztof Matyjaszewski 1, 2, 3, 4, 5
Affiliation  

For electrochemically mediated atom transfer radical polymerization (eATRP), novel mechanistic insights are formulated based on a two-compartment kinetic Monte Carlo model in which catalyst concentration gradients between a large “bulk” compartment away from the electrode and a very small compartment around the electrode are accounted for to reflect the concept of the Nernst diffusion layer. The mass transport of deactivator catalyst to the electrode and its electrochemical reduction at the electrode are treated separately to enable the model to explicitly distinguish between limitations of mass transport and limitations due to intrinsic chemical reactivity. The model is applied to eATRP of methyl acrylate at 298 K with CuIIBr2/Me6TREN (Me6TREN: tris((2-dimethylamino)ethyl)amine) and eATRP of n-butyl acrylate at 317 K with CuIIBr2/TPMA (TPMA: tris(2-pyridylmethyl)amine). Diffusional limitations on termination need to be accounted for to properly reflect the eATRP kinetics and the microstructural properties of the obtained polymers. In most cases, an eATRP with mixed chemical and mass transport control is obtained.

中文翻译:

电化学介导的ATRP的两室动力学Monte Carlo建模

对于电化学介导的原子转移自由基聚合(eATRP),基于两室动力学蒙特卡洛模型建立了新颖的力学见解,在该模型中,催化剂的浓度梯度在远离电极的大“本体”室和围绕电极的非常小室之间反映了能斯特扩散层的概念。钝化剂催化剂向电极的传质及其在电极上的电化学还原分别进行处理,以使模型能够明确地区分传质限制与固有化学反应性限制之间的区别。该模型适用于298 K下具有Cu II Br 2 / Me 6 TREN(Me 6的丙烯酸甲酯的eATRPTREN:三(((2-二甲基氨基)乙基)胺)和丙烯酸丁酯在317 K下与Cu II Br 2 / TPMA(TPMA:三(2-吡啶基甲基)胺)的eATRP 。必须考虑终止的扩散限制,以正确反映eATRP动力学和所得聚合物的微结构性质。在大多数情况下,可以获得具有混合化学和质量传输控制的eATRP。
更新日期:2018-09-25
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