Pleiotropic action of pH-responsive poly(pyridine/PEG) copolymers in the stabilization of silicic acid or the enhancement of its polycondensation

Abstract

In this paper the effect of two synthetic, pH-responsive co-polymers, U-PVPyPEGMA-H and Q-PVPyPEGMA-H, with pyridine and polyethylene glycol grafts, on silicic acid polymerization is presented. The scope of this work was to evaluate the impact of several experimental parameters, such as working pH, polymer MW, polymer concentration, state of the pyridine ring (non-protonated, protonated, quaternized) on the anticipated inhibitory and/or enhancement activity with regards to silicic acid autocondensation to produce amorphous silica. It was found that pH substantially influences the silicification reaction, either in the absence or presence of the polymers. pH also affects the protonation state of the pyridine N atom. For example, pH switching from 5.0 to 7.0 transforms U-PVPyPEGMA-H from a silica formation catalyst (pH = 5.0) to a silicic acid stabilizer (pH = 7.0). Concentration enhances the role of the polymers, either as silicic acid stabilizers or catalysts. Polymer MW appears to have no effect on their activity either as stabilizers or catalysts. Polymer entrapment in the precipitated amorphous silica matrix occurs under these experimental conditions, affecting particle size, morphology and tendency for aggregation. The state of the N atom on the pyridine ring (non-protonated, protonated, quaternized) exhibits a profound effect on silicic acid autocondensation to produce amorphous silica. Based on our results, a “free” (non-protonated) pyridine ring induces silica inhibition, whereas protonation or quaternization enhances silica formation.