A new copper(II) chloride/tris(2-piridylmethyl)amine (1/1) catalysed “Activators Regenerated by Electron Transfer” “Atom Transfer Radical Polymerisation” (ARGET ATRP) process for the polymerisation of styrene is described. The salient features of the method are the simultaneous use of ascorbic acid (reducing agent) and Na₂CO₃ (basic agent), the employment of a bifunctional initiator (ethyl 2,2-dichloropropionate) and the utilisation of a green solvent mixture composed of ethyl acetate and ethanol (AcOEt/EtOH). Na₂CO₃ plays a central role since not only preserves the ligand from protonation, but it can also activate the reducing agent. The quantity of monomer in the reaction mixture, the AcOEt/EtOH ratio and the load of ascorbic acid/carbonate are important factors for achieving a regular transformation. Working at 100 °C and with a metal load of only 0.025 mol%, an almost perfectly controlled telechelic polystyrene is produced, provided that conversion is kept below 50%. If conversion is higher, the control is gradually lost due superimposition of a step-growth process to the main chain polymerisation process. Two interesting phenomena, encountered during this study, are activation of the redox complex by using only Na₂CO₃ and gelation of polystyrene at 60 °C.

中文翻译：

---

铜催化的“通过电子转移再生的活化剂”，“双原子引发自由基聚合”的苯乙烯在醋酸乙酯/乙醇中的双功能引发剂，使用抗坏血酸/碳酸钠作为还原体系

描述了一种新的氯化铜（II）/三（2-吡啶基甲基）胺（1/1）催化的“通过电子转移再生的活化剂”“原子转移自由基聚合”（ARGET ATRP）工艺用于苯乙烯聚合。该方法的显着特征是同时使用抗坏血酸（还原剂）和Na ₂ CO ₃（碱性剂），使用双功能引发剂（2,2-二氯丙酸乙酯）和使用由绿色溶剂组成的混合物乙酸乙酯和乙醇（AcOEt / EtOH）。Na ₂ CO ₃由于不仅使配体不质子化，而且还可以活化还原剂，因此起着中心作用。反应混合物中单体的量，AcOEt / EtOH之比和抗坏血酸/碳酸盐的负载量是实现规则转化的重要因素。如果将转化率保持在50％以下，则在100°C的温度下工作且金属负载量仅为0.025 mol％，可以生产几乎完美控制的远螯聚苯乙烯。如果转化率较高，则由于逐步增长过程与主链聚合过程的叠加而逐渐失去控制。在这项研究中遇到的两个有趣的现象是，仅使用Na ₂ CO ₃活化氧化还原络合物，并在60°C下使聚苯乙烯凝胶化。