Department of Material and Life Chemistry, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan.
Chem Commun (Camb). 2013 Sep 28;49(75):8281-310. doi: 10.1039/c3cc43603a.
Conventional condensation polymerization proceeds in a step-growth polymerization manner, in which the generated polymers possess a broad molecular weight distribution, and control over molecular weight and polymer end groups is difficult. However, the mechanism of condensation polymerization of some monomers has been converted from step-growth to chain-growth by means of activation of the polymer end group, either due to the difference in substituent effects between the monomer and the polymer, or due to successive intramolecular transfer of catalyst to the polymer end. In this article, we review recent developments in chain-growth condensation polymerization (CGCP) in these two areas. The former approach has yielded many architectures containing aromatic polyamides and aromatic polyethers, with unique properties. In the latter case, the mechanism, catalysts, and initiators of Ni- and Pd-catalyzed coupling polymerizations leading to poly(alkylthiophene)s and poly(p-phenylene)s have been extensively investigated. Other well-defined π-conjugated polymers, such as polyfluorenes, n-type polymers, and alternating aryl polymers, have also been synthesized by means of catalyst-transfer condensation polymerization. Many π-conjugated polymer architectures prepared by utilizing catalyst-transfer condensation polymerization are not covered in this article.
常规缩合聚合以逐步聚合方式进行，所生成的聚合物具有较宽的分子量分布，且难以控制分子量和聚合物端基。然而，通过聚合物端基的活化，一些单体的缩合聚合机理已从逐步聚合转变为链式聚合，这要么是由于单体和聚合物之间的取代基效应的差异，要么是由于催化剂在聚合物端基上的连续分子内转移。本文综述了这两个领域中链增长缩合聚合（CGCP）的最新进展。前一种方法得到了许多含有芳香聚酰胺和芳香聚醚的具有独特性能的结构。在后一种情况下，Ni 和 Pd 催化偶联聚合导致聚（烷基噻吩）和聚（对亚苯基）的机理、催化剂和引发剂已被广泛研究。其他具有明确结构的π共轭聚合物，如聚芴、n 型聚合物和交替芳基聚合物，也通过催化剂转移缩合聚合合成。本文未涵盖利用催化剂转移缩合聚合制备的许多π共轭聚合物结构。
