Polystyrene grafting from silica nanoparticles via Nitroxide-Mediated-Polymerization (NMP): synthesis and SANS analysis with contrast variation method

TL;DR

This paper introduces an efficient method for grafting polystyrene onto silica nanoparticles using Nitroxide-Mediated Polymerization, and analyzes the resulting nanocomposites with contrast variation SANS to understand their structure.

Contribution

The study develops a new controlled grafting-from method for silica nanoparticles and applies contrast variation SANS for detailed structural analysis.

Findings

Successful synthesis of well-defined PS-silica nanoparticles.

Effective contrast variation SANS analysis of grafted nanoparticles.

Differences observed between hydrogenated and deuterated grafted chains.

Abstract

We present a new convenient and efficient "grafting from" method to obtain well defined polystyrene (PS) silica nanoparticles. The method, based on Nitroxide-Mediated Polymerization (NMP), consists to bind covalently the alkoxyamine, which acts as initiator controller agent, at the silica nanoparticles surface in two steps. The first step is a reaction between the aminopropylsilane and the silica particles in order to functionalize the particles surface with amino group. In a second step, the initiating-controlling alkoxyamine moiety is introduced via an over grafting reaction between the amino group and the N-hydroxysuccinimide based MAMA-SG1 activated ester. To simplify both their chemical transformation and the polymerization step, the native silica particles, initially dispersed in water, have been transferred in an organic solvent, the dimethylacetamide, which is also a good solvent for the polystyrene. The synthesis parameters have been optimized for grafting density, conversion rates, and synthesis reproducibility while keeping the colloidal stability and to avoid any aggregation of silica particles induced by the inter-particles interaction evolution during the synthesis. After synthesis, the final grafted objects have been purified and the non-grafted polymer chains formed in the solvent have been washed out by ultra filtration. Then the particles have been studied using Small angle Neutron Scattering (SANS) coupled to neutron contrast variation method. To optimize the contrast conditions, both hydrogenated and deuterated monomers have been used for the synthesis. A refined fitting analysis based on the comparison on two models, a basic core-shell and the Gaussian Pedersen model, enables us to fit nicely the experimental data for both the hydrogenated and deuterated grafted case. Differences are seen between grafting of normal or deuterated chains which can be due to monomer reactivity or to neutron contrast effect variations. The synthesis and the characterization method established in this work constitute a robust and reproducible way to design well defined grafted polymer nanoparticles. These objects will be incorporated in polymer matrices in a further step to create Nanocomposites for polymer reinforcement.