Barré Guillaume, Taton Daniel, Lastécouères Dominique, Vincent Jean-Marc
Laboratoire de Chimie Organique et Organométallique (UMR-CNRS 5802), Université Bordeaux 1, 351 cours de la Libération, 33405 Talence Cedex, France.
J Am Chem Soc. 2004 Jun 30;126(25):7764-5. doi: 10.1021/ja048096a.
The tetramine ligand 1 hexasubstituted by very long alkyl chains (C18H37) exhibits an exceptionally large temperature-dependent solubility in 1,4-dioxane, its solubility increasing ca. approximately 104-fold between 23 and 50 degrees C. The preformed copper(I) complex CuBr/1 was shown to catalyze the atom transfer radical polymerization of methyl methacrylate with good control of the molar masses and polydispersities. Due to the thermoresponsive character of CuBr/1 polymerizations were carried out in homogeneous conditions while lowering the temperature to 10 degrees C led to the precipitation of the catalyst. Catalyst recovery was achieved with high yield ( approximately 95%) by a simple filtration under noninert atmosphere. Very low residual copper contamination ( approximately 200 ppm) was measured in the final polymer. The catalyst was recycled two times without significant loss of activity.
由非常长的烷基链（C18H37）六取代的四胺配体1在1,4 - 二氧六环中表现出异常大的温度依赖性溶解度，其溶解度在23至50摄氏度之间增加约104倍。预制的铜（I）配合物CuBr/1被证明能催化甲基丙烯酸甲酯的原子转移自由基聚合反应，对摩尔质量和多分散性有良好的控制。由于CuBr/1的热响应特性，聚合反应在均相条件下进行，而将温度降至10摄氏度会导致催化剂沉淀。通过在非惰性气氛下简单过滤，催化剂回收率很高（约95%）。在最终聚合物中测得的残留铜污染非常低（约200 ppm）。该催化剂循环使用了两次，活性没有明显损失。
