Preparation of (Ba,Sr)TiO3@polystrene core-shell nanoparticles by solvent-free surface-initiated atom transfer radical polymerization

Abstract

The polystyrene shells have been successfully grown on the barium strontium titanate (BST) nanocrystals, which were synthesized by microwave-activated glycothermal method, via a solvent-free surface-initiated atom transfer radical polymerization (SI-ATRP) after the 2-bromo-2-methylpropionic acid molecules (Br-MPA) were anchored at the surface of BST nanocrystals through ligand exchange with hydroxyl groups on their surfaces. These surface modified BST nanocrystals can then be perfectly dispersed in styrene monomer and act as macroinitiators for ATRP to yield BST@PS core-shell structured nanoparticles, which endow the BST nanocrystals with exceptionally good dispersibility and stability in hydrophobic solvents. The BST@PS core-shell structures were characterized by X-ray diffraction (XRD) technique and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (Raman), differential scanning calorimetry (DSC) and gel permeation chromatography were also employed to probe the Br-MPA and PS on the BST nanocrystals. It has been shown that after the BST nanocrystals are surface-modified with Br-MPA, the polymerization of styrene can steadily occur at the surface of BST nanocrystals to form a uniform polystyrene shell and its thickness can reach ∼10nm when the polymerization reaction is extended to 36h, while no changes are found to take place with the BST nanocrystals. Compared with typical high molecular weight PS (Mn=6700), the as-obtained PS possess a relatively low molecular weight (Mn=5473) and a lower glass transition temperature (Tg∼93°C). The research results demonstrate a viable strategy for the preparation of polymer-coated functional metal oxides nanocrystals, potentially useful in biological and nanoelectronic applications.