The Molecular Foundry, E. O. Lawrence Berkeley National Laboratory, MS 67R6110, Berkeley, CA 94720-8139, USA.
J Chromatogr A. 2010 Feb 5;1217(6):902-24. doi: 10.1016/j.chroma.2009.09.073. Epub 2009 Oct 2.
The porous polymer monoliths went a long way since their invention two decades ago. While the first studies applied the traditional polymerization processes at that time well established for the preparation of polymer particles, creativity of scientists interested in the monolithic structures has later led to the use of numerous less common techniques. This review article presents vast variety of methods that have meanwhile emerged. The text first briefly describes the early approaches used for the preparation of monoliths comprising standard free radical polymerizations and includes their development up to present days. Specific attention is paid to the effects of process variables on the formation of both porous structure and pore surface chemistry. Specific attention is also devoted to the use of photopolymerization. Then, several less common free radical polymerization techniques are presented in more detail such as those initiated by gamma-rays and electron beam, the preparation of monoliths from high internal phase emulsions, and cryogels. Living processes including stable free radicals, atom transfer radical polymerization, and ring-opening metathesis polymerization are also discussed. The review ends with description of preparation methods based on polycondensation and polyaddition reactions as well as on precipitation of preformed polymers affording the monolithic materials.
多孔聚合物整体材料自二十年前发明以来已经取得了很大的进展。虽然最初的研究应用了当时为制备聚合物颗粒而建立的传统聚合工艺，但对整体结构感兴趣的科学家的创造力后来导致了许多不常见技术的应用。本文综述了众多新兴方法。本文首先简要描述了用于制备包含标准自由基聚合的整体材料的早期方法，并将其发展至今。特别关注了工艺变量对多孔结构和孔表面化学形成的影响。特别关注光聚合的使用。然后，更详细地介绍了几种不太常见的自由基聚合技术，如γ射线和电子束引发聚合、高内相乳液制备整体材料以及冷冻凝胶。还讨论了稳定自由基、原子转移自由基聚合和开环易位聚合等活态聚合过程。综述最后描述了基于缩聚和加成聚合反应以及预聚物沉淀制备整体材料的方法。
