Methacrylic Acid Based Polymer Networks with a High Content of Unfunctionalized Nanosilica: Particle Distribution, Swelling, and Rheological Properties

Abstract

The poor stability and tendency to agglomerate of unfunctionalized nano-SiO₂ in the presence of ionic species presents a challenge for preparing poly­(methacrylic acid)/nano-SiO₂ nanocomposite (NC) hydrogels with desired strength and swelling capability. We proposed a facile and eco-friendly method for the preparation of PMAA/SiO₂ NC hydrogels using unfunctionalized silica nanoparticles (NPs) in the form of a suspension. SEM and TEM analyses showed that the NP distribution in the polymer matrix highly depended on the particle concentration. At lower concentrations (up to 13.9 wt %), the NPs were uniformly dispersed as single nanoparticles. With an increase in NP concentration, homogeneously dispersed nanoscale aggregates were formed, while a further increase in the silica concentration led to the formation of homogeneous structures consisting of mutually interacting nanosilica particles coated with PMAA. Swelling experiments confirmed that the silica NPs behaved as adhesive fillers that interacted with PMAA chains, causing the formation of a thin polymer layer strongly adsorbed at the particle interface. The thicknesses of the adsorbed polymer layer, as well as the swelling kinetic parameters, were strongly influenced by nanoparticle size and concentration. Combining nanosilica and PMAA in the form of a soft hydrogel network provided stabilization of the NPs and ensured better mechanical properties of the obtained NC hydrogels compared to pure polymer matrix. The optimal loadings, necessary to ensure the most improved dynamical-mechanical properties, were found in the case of the formation of homogeneously dispersed, nanosized silica aggregates in a PMAA matrix