Poly(ethylene oxide) grafted silica nanoparticles: efficient routes of synthesis with associated colloidal stability

In this study, poly(ethylene oxide) monomethyl ether (MPEO) of molecular weight of 5000, 10 000, and 20 000 g mol-1 were grafted onto colloidal silica nanoparticles (NPs) of a 27.6 nm diameter using two distinct "grafting to" processes. The first method was based on the coupling reaction of epoxide-end capped MPEO with amine-functionalized silica NPs, while the second method was based on the condensation of triethoxysilane-terminated MPEO onto the unmodified silica NPs. The influence of PEO molecular weight, grafting process and grafting conditions (temperature, reactant concentration, reaction time) on the PEO grafting density was fully investigated. Thermogravimetric analysis (TGA) was used to determine the grafting density which ranged from 0.12 chains per nm2 using the first approach to 1.02 chains per nm2 when using the second approach. 29Si CP/MAS NMR characterization indirectly revealed that above a grafting density value of 0.3 PEO chains per nm2, a dendri-graft PEO network was built around the silica surface which was composed of PEO chains directly anchored to the silica surface and those grafted to silica NPs by intermediate of >CH-O-Si- bonds. The colloidal stability of the particles during different steps of the grafting process was characterized by small-angle X-ray scattering (SAXS). We have found that the colloidal systems are stable whatever the achieved grafting density due to the strong repulsions between the NPs, with the strength of repulsion increasing with the molecular weight of the grafted MPEO chains.