Extraordinary Adhesion of Phenylboronic Acid Derivatives of Polyvinylamine to Wet Cellulose: A Colloidal Probe Microscopy Investigation

Typically, the adhesion between cellulose surfaces under aqueous conditions is very poor. Often, adsorbed polymers such as polyvinylamine (PVAm) are used to increase the wet strength; however, this provides only a minimal increase in the adhesion energy. Here, the adhesion between cellulose surfaces with adsorbed layers of phenylboronic acid derivatized polyvinylamine has been studied using colloidal probe microscopy as a function of pH. The adhesion due to the phenylboronic acid (PBA) groups grafted on the polyvinylamine backbone is almost 30 times greater, providing a new, exciting class of polymers using covalent linkages to improve the strength of the joint between cellulose surfaces. The measured surface forces on approach provided key information on the molecular conformation of the polymers at the cellulose-solution interface. At low pH, the three polymers tested, PVAm, PVAm-Ph (with pendant phenol groups), and PVAm-PBA (with phenylboronic acid groups) all had a relatively flat conformation at the interface, which is in agreement with the predictions based upon theory for highly charged polyelectrolytes adsorbing to an oppositely charged interface. With increasing pH, the charge on the polymers is reduced, eventually resulting in a more expansive conformation at the interface at pH 10 and above with the development of a steric interaction force. The onset of this steric force correlates well with the observed significant increase in the pull-off force upon separation of the cellulose surfaces. Furthermore, a greater increase in the adhesion was observed for PVAm-PBA in agreement with previous studies using macroscopic cellulose surfaces. This is attributed to the formation of boronic acid esters between the polymer and the cis diol groups on the cellulose surface.