Toward Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer (eRAFT) Polymerization: Can Propagating Radicals Be Efficiently Electrogenerated from RAFT Agents?

Lorandi Francesca; Fantin Marco; Shanmugam Sivaprakash; Wang Yi; Isse Abdirisak A.; Gennaro Armando; Matyjaszewski Krzysztof

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Toward Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer (eRAFT) Polymerization: Can Propagating Radicals Be Efficiently Electrogenerated from RAFT Agents?

机译：朝向电化学介导的可逆添加 - 破碎链转移（Elaft）聚合：可以从筏剂中有效地发射自由基吗？

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Electrochemistry provides easily tunable parameters for the preparation of well-defined polymers in a spatiotemporal controlled manner under mild conditions. This work discusses the requisites for an electrochemically mediated reversible addition-fragmentation chain-transfer (eRAFT) polymerization, in which electrochemical stimuli are used to reduce the RAFT agent, either directly or in the presence of a mediator. The redox properties of several RAFT agents were investigated by cyclic voltammetry and correlated to their structures. The direct electrolysis of RAFT agents in the presence of a monomer caused the loss of RAFT agents, thus leading to uncontrolled polymerizations. These issues could partially be overcome by using a mediator that shuttles the electrons from the electrode to the RAFT agent in solution. Several compounds were tested to define the characteristics of suitable mediators.

机译：电化学在温和条件下，在温和的条件下，可以以时尚的控制方式制备明确定义的聚合物的容易可调谐参数。该作品讨论了电化学介导的可逆添加 - 碎片链转移（Elaft）聚合的必要条件，其中使用电化学刺激用于在介体的存在下或在介质存在下减少筏剂。通过循环伏安法研究了几种筏剂的氧化还原性能并与其结构相关。在单体存在下筏剂的直接电解导致筏剂的损失，从而导致不受控制的聚合。通过使用将来自电极从电极从电极穿梭到溶液中的筏剂的介体可以部分地克服这些问题。测试了几种化合物以定义合适的介质的特征。

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《Macromolecules》 |2019年第4期|共10页
作者
Lorandi Francesca; Fantin Marco; Shanmugam Sivaprakash; Wang Yi; Isse Abdirisak A.; Gennaro Armando; Matyjaszewski Krzysztof;
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Carnegie Mellon Univ Dept Chem 4400 Fifth Ave Pittsburgh PA 15213 USA;

Carnegie Mellon Univ Dept Chem 4400 Fifth Ave Pittsburgh PA 15213 USA;

Carnegie Mellon Univ Dept Chem 4400 Fifth Ave Pittsburgh PA 15213 USA;

Carnegie Mellon Univ Dept Chem 4400 Fifth Ave Pittsburgh PA 15213 USA;

Univ Padua Dept Chem Sci Via Marzolo 1 I-35131 Padua Italy;

Univ Padua Dept Chem Sci Via Marzolo 1 I-35131 Padua Italy;

Carnegie Mellon Univ Dept Chem 4400 Fifth Ave Pittsburgh PA 15213 USA;

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正文语种 eng
中图分类高分子化学（高聚物）;
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1. Toward Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer (eRAFT) Polymerization: Can Propagating Radicals Be Efficiently Electrogenerated from RAFT Agents? [J] . Lorandi Francesca, Fantin Marco, Shanmugam Sivaprakash, Macromolecules . 2019,第4期

机译：朝向电化学介导的可逆添加 - 破碎链转移（Elaft）聚合：可以从筏剂中有效地发射自由基吗？
2. alpha-Cyanobenzyl dithioester reversible addition-fragmentation chain-transfer agents for controlled radical polymerizations [J] . Li CZ, Benicewicz BC Journal of Polymer Science, Part A. Polymer Chemistry . 2005,第7期

机译：用于受控自由基聚合的α-氰基苄基二硫酯可逆加成-断裂链转移剂
3. Controlled Free-Radical Copolymerization of Maleic Anhydride and Divinyl Ether in the Presence of Reversible Addition-Fragmentation Chain-Transfer Agents [J] . A. V. Serbin, E. N. Karaseva, I. V. Dunaeva Polymer science, Series B. Rapid communications reviews . 2011,第3a4期

机译：可逆加成-断裂链转移剂存在下马来酸酐和二乙烯基醚的受控自由基共聚
4. Recent Advances in Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer (RAFT Process) [C] . San H. Thang Controlled Polymer Synthesis: New Approaches in Applications and Processes . 2001

机译：可逆加成-断裂链转移（RAFT工艺）在自由基聚合中的最新进展
5. Enhancing control of macromolecular architecture by synergistic combination of atom transfer radical polymerization, nitroxide mediated polymerization, and reversible addition-fragmentation chain transfer polymerization. [D] . Nicolay, Renaud. 2010

机译：通过原子转移自由基聚合，氮氧化物介导的聚合和可逆加成-断裂链转移聚合的协同组合，增强对大分子结构的控制。
6. Electrochemically Mediated Reversible Addition–Fragmentation Chain-Transfer Polymerization [O] . Yi Wang, Marco Fantin, Sangwoo Park, -1

机译：电化学介导的可逆加成-断裂链转移聚合
7. Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible AdditionFragmentation Chain Transfer Polymerization [O] . -1

机译：蒽醌介导的三碳酸甘油链转移剂的还原以引发电化学可逆添加额外链转移聚合
8. Reversible Addition-Fragmentation Chain Transfer (RAFT) Copolymerization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers (Postprint). [R] . Ramirez, S. M., Diaz, Y. J., Sahagun, C. M., 2013

机译：可逆加成 - 断裂链转移（RaFT）共聚合氟烷基多面体低聚倍半硅氧烷（F-pOss）大分子单体（postprint）。

Toward Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer (eRAFT) Polymerization: Can Propagating Radicals Be Efficiently Electrogenerated from RAFT Agents?

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