Porous polymer monoliths: amazingly wide variety of techniques enabling their preparation.

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.