Porosity inherent to chemically crosslinked polymers. Poly(N-vinylimidazole) hydrogels.

Swollen polymer networks exhibit multiscale pores filled with solvent. Such porosity, inherent to cross-linked polymers, determines some of their most relevant physical properties and applications. In this research, several samples of chemically crosslinked poly(N-vinylimidazole) were synthesized with the same permanent crosslinking density at two different conversions, and their inherent porosity was characterized on freeze-dried specimens by SEM, TEM and nitrogen physisorption. It was thus found that all of the samples showed pores, both on the nanometer and the micrometer scales, whose dimensions were mostly equal to or larger than the mesh size of the primary polymer network (22 nm) and whose volume and specific surface decreased with increasing conversion. Micropores have, in all cases, a very minor contribution. Samples synthesized with the largest comonomer concentrations show quasi-spherical mesopores (90 nm average diameter at any conversion) and macropores (from 5 to 10 microm with increasing conversion), whereas the mesopores of samples synthesized with the largest crosslinker ratios were channel-like (150 nm) and the macropores were interconnected contiguous voids (3 microm). Samples with intermediate compositions exhibit the lowest porosity due, mostly, to interconnected mesopores. The differences in shape were ascribed to the mechanism of phase separation, taking place during polymerization, even for samples that are transparent following polymerization. The inherent porosity is a significant source of spatial inhomogeneity, which contributes to the increase in turbidity. Light scattering decreases with increasing ionization when the degree of protonation is greater than 10%. An important consequence of the inherent porosity is that the degrees of swelling determined either gravimetrically or through size measurements are not equivalent.