The coordination−insertion ring-opening polymerization of ε-caprolactone was initiated from
amine or hydroxyl groups spread over the surface of silica (ca. 30 nm) or cadmium sulfide (ca. 1.5 nm)
nanoparticles, respectively. The initiation selectively occurred from the surface functional groups after
activation into aluminum alkoxides species. The covalent grafting of the polyester chains was confirmed
by the solubilization of the nanoparticles in organic solvents, e.g., CHCl3 and THF for silica nanoparticles
and toluene for CdS nanoparticles, at least when the surface-grafted PCL chains were long enough. In
the case of silica nanoparticles, the linear dependence of the PCL molar mass as determined by 1H NMR
analysis on the initial monomer-to-amine ratio confirmed the controlled character of the polymerization.
Transmission electron microscopy of thin films of PCL-grafted CdS revealed an homogeneous dispersion
of the semiconducting nanoparticles throughout the polyester matrix.
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