Hydrazide-Derivatized Microgels Bond to Wet, Oxidized Cellulose Giving Adhesion Without Drying or Curing

摘要

Hydrazide-derivatized poly(N-isopropylacrylamide-co-acrylic acid) microgels gave strong adhesion to wet, TEMPO oxidized, regenerated cellulose membranes without a drying or heating step. Adhesion was attributed to hydrazone covalent bond formation with aldehyde groups present on the cellulose surfaces. This is one of only three chemistries we have found that gives significant never-dried adhesion between wet cellulose NI surfaces. By contrast, for cellulose joints that have been dried and heated before wet testing, the hydrazide-hydrazone chemistry offers no advantages over standard paper industry wet strength resins. The design rules for the hydrazide-microgel adhesives include: cationic microgels are superior to anionic gels; the lower the microgel cross-link density, the higher the adhesion; longer PEG-based hydrazide tethers offer no advantage over shorter attachments; and, adhesion is independent of microgel diameter. Many of these rules were in agreement with predictions of a simple adhesion model where the microgels were assumed to be ideal springs. We propose that the unexpected, high cohesion between neighboring microgels in multilayer films was a result of bond formation between hydrazide groups and residual NHS-carboxyl esters from the preparation of the hydrazide microgels.