Determination of Reaction Kinetics by Time-Resolved Small-Angle X-ray Scattering during Polymerization-Induced Self-Assembly: Direct Evidence for Monomer-Swollen Nanoparticles

The kinetics of heterogeneous polymerization is determined directly using small-angle X-ray scattering (SAXS). This important advancement is exemplified for the synthesis of sterically-stabilized diblock copolymer nanoparticles by reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) in mineral oil at 90 degrees C. The principle of mass balance is invoked to derive a series of equations for the analysis of the resulting time-resolved SAXS patterns. Importantly, there is a continuous change in the X-ray scattering length density for the various components within the reaction mixture. This enables the volume fraction of unreacted BzMA monomer to be calculated at any given time point, which enables the polymerization kinetics to be monitored in situ directly without relying on supplementary characterization techniques. Moreover, SAXS enables the local concentration of both monomer and solvent within the growing swollen nanoparticles to be determined during the polymerization. Data analysis reveals that the instantaneous rate of BzMA polymerization is proportional to the local monomer concentration within the nanoparticles. In principle, this powerful new time-resolved SAXS approach can be applicable to other heterogeneous polymerization formulations. A generic SAXS model for polymerization-induced self-assembly (PISA) formulations has been developed by applying the law of conservation of mass. Time-resolved small-angle X-ray scattering (SAXS) data are analyzed to determine the kinetics of polymerization directly during the synthesis of spherical nanoparticles. This new analytical approach enables calculation of the mass transport of monomer and solvent in and out of the growing nanoparticles.image