Influence of Functional Group Concentration on Hypercrosslinking of Poly(vinylbenzyl chloride) PolyHIPEs: Upgrading Macroporosity with Nanoporosity.

With the aim to study the influence of monomer ratio in poly(high internal phase emulsions) (polyHIPEs) on the polymer network architecture and morphology of poly(vinylbenzyl chloride-co-divinylbenzene-co-styrene) after hypercrosslinking via the internal Friedel-Crafts process, polyHIPEs with 80% overall porosity were prepared at three different initial crosslinking degrees, namely 2, 5, and 10 mol.%. All had typical interconnected cellular morphology, which was not affected by the hypercrosslinking process. Nitrogen adsorption and desorption experiments with BET and t-plot modelling were used for the evaluation of the newly introduced nanoporosity and in combination with elemental analysis for the evaluation of the extent of the hypercrosslinking. It was found that, for all three initial crosslinking degrees, the minimum amount of functional monomer, 4-vinylbenzyl chloride, was approximately 30 mol.%. Hypercrosslinking of polymers with lower concentrations of functional monomer did not result in induction of nanoporosity while the initial crosslinking degree had a much lower impact on the formation of nanoporosity.