Aqueous Fabrication of pH-Gated, Polymer-Brush-Modified Alumina Hybrid Membranes

In this Article, we studied the surface immobilization of five organic-acid-modified atom-transfer radical polymerization (ATRP) initiators based on salicylic acid, catechol, phthalic acid, and m- and p-benzoic add on alumina, and we also investigated the growth of hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(poly(ethylene glycol)methycrylate) (PPEGMA(6)) brushes from the resulting initiator-modified substrates. Whereas the surface immobilization of phthalic acid- and benzoic acid-based initiators results in only very thin brushes or no brush growth at all, S1-ATRP of HEMA and PEGMA(6) from alumina surfaces modified with salicylate or catechol generates brushes with thicknesses comparable to those obtained using organosilane-based initiators. Most interestingly, the surface immobilization of the catechol- and salicylate based-initiators was found to be pH dependent, which allowed facile variation of the ATRP initiator surface concentration and, concomitantly, the polymer brush grafting density by adjusting the pH of the aqueous solution that was used to immobilize the initiator. This is in contrast to organosilane-based initiators, where the variation of the grafting density is usually accomplished using mixtures of the ATRP initiator and an ATRP inactive "dummy". Another difference between the organosilane-based initiators and the organic acid analogues is the stability of hydrophilic brushes grown from alumina. After a certain threshold thickness was exceeded, organosilane-tethered PPEGMA(6) brushes were observed to detach from the substrate, in contrast to brushes grown from catechol or salicylate initiators, which did not show signs of degradation. Finally, as a first proof-of-concept, the salicylate-based initiator was used to develop an all-aqueous protocol for the modification of alumina membranes with hydrophilic PHEMA and succinic anhydride post-modified polymer brushes. The water permeation properties of these hybrid membranes can be controlled by adjusting the brush thickness in the case of the neutral PHEMA brush coating or can be pH-gated after post-polymerization modification to introduce carboxylic acid groups.