The Porogen

The porogen is the solvent used for dissolving the monomers, the template and the initiator. The porogen is also responsible for the creation of the pores in the polymer, and thus also affects the surface area. In non-covalent molecular imprinting, the porogen is usually chosen so that it promotes the interactions between 

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In the multistep swelling and polymerization method, polymerization time, temperature, and initiator concentration have marginal effects only. The ratio of monovinyl to divinyl monomer in the polymerization mixture, along with the composition of the porogenic systems, is known to be the most important factor in controlling the ultimate macroporous structure. The average molecular... 

Other microporous materials have been synthesized using the porogen polyethylene glycol in polyethylene oxide-urethane gels [27]. Micropores were formed in the gel, and it was found that the diffusion of larger species, vitamin B12, was enhanced relatively more than that of a smaller species, proxyphylline. This result is in qualitative agreement with that found for electrophoretic transport by RiU et al. [322] discussed earher, where the mobility of larger species was preferentially enhanced in the templated media. 

Fig. 3. Effect of dodecanol in the porogenic solvent on the differential pore size distribution of molded poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths (Reprinted with permission from [62]. Copyright 1996 American Chemical Society). Conditions polymerization time 24 h, temperature 70 °C, polymerization mixture glycidyl methacrylate 24%, ethylene dimethacrylate 16%, cyclohexanol and dodecanol contents in mixtures 60/0 (curve 1), 57/3 (curve 2), 54/6 (curve 3), and 45/15 vol.% (4)...

The morphology of the monoliths is closely related to their porous properties, and is also a direct consequence of the quality of the porogenic solvent as well as the percentage of crosslinking monomer and the ratio between the monomer and porogen phases. The presence of synergistic effects of these reaction conditions was verified using multivariate analysis [65]. 

After pre-treatment, the monolithic mixture consisting of the monomers, cross-linker, initiator, and the porogenic solvents is filled into the capillary and then sealed at both ends. 

As being indicated above, the resulting overall porosity of the monolithic polymer can be influenced and controlled by the nature and composition of the porogenic solvent as well as the amount of... 

Since the ability of the porogen or a porogen mixture to dissolve a certain polymer system can usually hardly be estimated without experimentation, the effect of porogens on the overall porosity of monolithic materials is widely empirical. 

The fact that adding a better solvent to the mixture results in a shift of the distribution to smaller pore sizes has been explained by the mechanism of pore formation, postulated for macroporous resins in the late 1960s [101-103]. The addition of a poor solvent causes the phase separation to occur early, whereas the precipitated polymer nuclei are swollen with monomers, which present a better solvating agent than the porogen. Due to the high monomer concentration within the globuli. 

The results of the MIP analyses of the bulk polymers are illustrated in Figure 1.7. It could be demonstrated that the polymerization time is capable of influencing the shape of the pore distribution itself, rather than shifting a narrow macropore distribution (and thus the pore-size maximum) along the scale of pore diameter (see effect of the porogenic solvent in Section 1.3.2.2 and Figure 1.5). On... 

The in situ polymerisation consists of filling a capillary or a column with the prepolymerisation mixture containing the template, the functional monomer, the crosslinker, the initiator and the porogenic solvent (Fig. 11). Then the column is heated or submitted to UV radiation for polymerisation. In the in situ thermally initiated polymerisation process, the tube with the pre-polymerisation mixture is submerged in a controlled-temperature water bath, whereas for in situ photoinitiated polymerisation, a UV-transparent capillary or column is needed. The resulting continuous rod of polymer is washed with an appropriate solvent to remove the template and the excess of monomer. 

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