Intramolecular olefin metathesis as a robust tool to synthesize single-chain nanoparticles in a size-controlled manner

Abstract

A comprehensive examination of the synthesis of single-chain nanoparticles (SCNPs) from statistical copolymers of n-butyl methacrylate (BMA) and 3-butenyl methacrylate (3BMA), i.e., P(BMA-co-3BMA)s, via the intramolecular olefin metathesis reaction under high dilution conditions is described. The olefin metathesis reaction of P(BMA-co-3BMA) using Grubbs’ 2^nd generation catalyst in CH₂Cl₂ efficiently gave the corresponding SCNPs under mild conditions. We achieved the size-controlled synthesis of the SCNPs by adjusting the following factors: (1) the olefin content in the precursor, (2) the molecular weight of the precursor, and (3) the solvent quality of the reaction medium. The hydrodynamic radius and the intrinsic viscosity of the resultant SCNPs were investigated by DLS and viscometric measurements, respectively, which provided further evidence of SCNP formation with controlled diameters. Furthermore, the above-established intramolecular olefin metathesis approach was successfully applied to poly(acrylate), poly(styrene), and poly(ester) precursors, which proved that the present approach could be applied to a wide range of olefin-containing precursors to give SCNPs with various functional groups.