Crosslinking of Pressure-Sensitive Adhesives with Polymer-Grafted Nanoparticles

Nanocomposite filler particles provide multiple routes to mechanically reinforce pressure-sensitive adhesives (PSAs), as their large surface area to volume ratios provide a means of effectively crosslinking multiple polymer chains. A major advancement could therefore be enabled by the design of a particle architecture that forms multiple physical and chemical interactions with the surrounding polymer matrix, while simultaneously ensuring particle dispersion and preventing particle aggregation. Understanding how such multivalent interactions between a nanoparticle crosslinking point and the PSA polymer affect material mechanical performance would provide both useful scientific knowledge on the mechanical structure-property relationships in polymer composites, as well as a new route to synthesizing useful PSA materials. Herein, we report the use of polymer-grafted nanoparticles (PGNPs) composed of poly(n-butyl acrylate-co-acrylic acid) chains grafted to SiO₂ nanoparticle (NP) surfaces to cohesively reinforce PSA films against shear stress without compromising their adhesive properties. The use of acrylic acid-decorated PGNPs allows for ionic crosslinking via metal salt coordination to be used in conjunction with physical entanglement, yielding 33% greater shear resistance and up to 3-fold longer holding times under static load. In addition, the effects of material parameters such as PGNP/crosslinker loading, polymer graft length, and core nanoparticle size on mechanical properties are also explored, providing insights into the use of PGNPs for the rational design of polymer composite-based PSAs.