Pintauer Tomislav, Matyjaszewski Krzysztof
Duquesne University, Department of Chemistry and Biochemistry, 600 Forbes Avenue, 308 Mellon Hall, Pittsburgh, PA 15282, USA.
Chem Soc Rev. 2008 Jun;37(6):1087-97. doi: 10.1039/b714578k. Epub 2008 Apr 24.
Over the past decade, copper-catalyzed atom transfer radical polymerization (ATRP) has had a tremendous impact on the synthesis of polymeric materials with well defined compositions, architectures and functionalities. Apart from synthetic aspects of ATRP, considerable effort has also been devoted to structural and mechanistic understanding of copper complexes involved in ATRP, as well as development of methodologies to decrease the amount of catalyst needed in these systems. This tutorial review reports on recent advances in the area of catalyst regeneration in ATRP and mechanistically similar atom transfer radical addition (ATRA) using environmentally benign reducing agents. The outlined processes termed ARGET (activators regenerated by electron transfer) and ICAR (initiators for continuous activator regeneration) ATRP enable the synthesis of well-defined (co)polymers and single addition adducts using very low concentrations of copper catalysts (1-100 ppm). Recent developments in this area could have profound industrial implications on the synthesis of well-defined polymeric materials and small organic molecules.
在过去十年中，铜催化的原子转移自由基聚合（ATRP）对合成具有明确组成、结构和功能的聚合物材料产生了巨大影响。除了ATRP的合成方面，人们还投入了大量精力来深入了解参与ATRP的铜配合物的结构和机理，以及开发减少这些体系中所需催化剂量的方法。本教程综述报道了在使用环境友好型还原剂的ATRP和机理类似的原子转移自由基加成（ATRA）中催化剂再生领域的最新进展。概述的称为ARGET（通过电子转移再生的活化剂）和ICAR（连续活化剂再生的引发剂）ATRP的过程，能够使用非常低浓度的铜催化剂（1 - 100 ppm）合成明确的（共）聚合物和单加成加合物。该领域的最新进展可能对明确聚合物材料和有机小分子的合成产生深远的工业影响。
