Stopped-flow kinetics of pH-responsive polyamine latexes: how fast is the latex-to-microgel transition?

Four poly(ethylene glycol)-stabilized polyamine latexes, namely, poly(2-vinylpyridine) (P2VP), poly(2-(tert-butylamino)ethyl methacrylate) (PTBAEMA), poly(2-(diethylamino)ethyl methacrylate) (PDEA), and poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) were prepared via emulsion copolymerization using divinylbenzene (DVB) as a cross-linker at 0.80 mol % for all formulations. According to dynamic light scattering studies, the resulting latexes were near-monodisperse and had approximately constant hydrodynamic diameters of 205-220 nm at pH 10; a latex-to-microgel transition was observed at around the respective pKa of each polyamine on addition of acid. The kinetics of swelling of each latex was investigated by the pH-jump method using a commercial stopped-flow instrument. The most rapid swelling was observed for the P2VP latex, which exhibited a characteristic swelling time (t*) of 5 ms. The corresponding t* values for PTBAEMA and PDEA were 25 and 35 ms, respectively, whereas the PDPA particles exhibited significantly slower swelling kinetics (t* = 180 ms). These t* values could not be correlated with either the latex Tg or the polyamine pKa. However, there is a positive correlation between t* and the repeat unit mass of the amine monomer, which suggests that the cationic charge density of the protonated polymer chains may influence the kinetics of swelling. Alternatively, the observed differences in swelling kinetics may simply reflect subtle differences in the DVB cross-link density, with more uniformly cross-linked latexes being capable of responding more quickly to a pH jump. The kinetics of deswelling for the corresponding microgel-to-latex transition was also briefly investigated for the PTBAEMA and P2VP particles. In both cases, much slower rates of deswelling were observed. This suggests that a latexlike "skin" is formed on the outer surface of the microgel particles during their deprotonation, which significantly retards the excretion of both salt and water.