No abstract

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 γ-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.

Monolithic columns for capillary electrochromatography have been prepared within the confines of untreated fused-silica capillaries in a single step by a simple copolymerization of mixtures of butyl methacrylate, ethylene dimethacrylate, and 2-acrylamido-2-methyl-1-propane-sulfonic acid (AMPS) in the presence of a porogenic solvent. The use of these novel macroporous monoliths eliminates the need for frits, the difficulties encountered with packed capillaries, and capillary surface functionalization. Since the porous properties of the monolithic materials can be easily tailored through changes in the composition of the ternary porogenic solvent, the effects of both pore size and the percentage of sulfonic acid monomer on the efficiency and the electroosmotic flow velocity of the capillary columns could be studied independently over a broad range. A simple increase in the content of charged functionalities within the monolith leads to an expected acceleration of the flow velocity. However, increasing the pore size leads to a substantial deterioration of the efficiency of the separation. In contrast, monoliths with increasing levels of AMPS in which the pore size remains fixed due to adjustments in the composition of the porogenic solvent show no deterioration in efficiency while maintaining the same increase in flow velocity, thus producing a significant reduction in separation time. Additionally, measurements on monoliths with constant levels of AMPS but different pore sizes suggest that flow velocity may be affected by the flow resistance within the capillary column.

Reactive polymers play many roles, from supports for solid-phase synthesis or catalysis to media for separations. Although macroporous polymer beads that provide high reactive capacities and excellent solvent tolerance are well established, approaches to monosized beads with optimized pore structures or multiple chemistries segregated within pores of different sizes have expanded their realm of application. Polymer monoliths containing intricate pore networks can be obtained in any desired shape by a simple molding process and provide unique advantages such as fast kinetics, high reactivity, and high throughput. Applications ranging from immobilized enzyme reactors to fast media for the separation of synthetic or biopolymers are presented.