Effect of solvent quality and chain confinement on the kinetics of polystyrene bromination

We report on the kinetics of the bromination of free polystyrene (PS) chains in bulk solution and those anchored on flat solid substrates by performing the bromination reaction in different solvents, including nitrobenzene (NB), 1-chlorodecane (CD), 1-chloroundecane (CUD), and 1-chlorododecane (CDD), at various temperatures. We find that bulk bromination of PS follows the second-order kinetic in bromine and the reaction rate increases with increasing dielectric constant of the solvent (E). In spite of epsilon(CDD) > epsilon(CD), the bulk bromination kinetics of PS in CDD is slower than that in CD because of lower Solubility of PS in CDD than in CD. In addition, we demonstrate that the reaction rates for brominating PS brushes anchored to flat solid substrates are much slower than those for brominating free PS chains in bulk Solution. We attribute this behavior to steric hindrance due to PS confinement on the substrate.