Gelation in Living Copolymerization of Monomer and Divinyl Cross-Linker: Comparison of ATRP Experiments with Monte Carlo Simulations

Abstract

Two types of Monte Carlo simulations were carried out to simulate gelation in a living copolymerization of monovinyl monomer and divinyl cross-linker. The simulated gel points under various conditions were compared to the experimental gel points obtained in series of ATRP reactions and the calculated gel points based on Flory−Stockmayer (FS) theory. The first simulation was based on an off-lattice (OL) model, simplified by ignoring the geometry of macromolecules. The second more complex simulation was based on the dynamic lattice liquid (DLL) model. Both OL model and FS mean-field theory were capable to count on the influence of molar ratios of cross-linker to initiator and initiation rate on the gel points. However, the simulated gel points occurred at much lower monomer conversion, as compared to the experimental results. Furthermore, the solvent dilution, an important parameter to adjust the experimental gel points, had no effect on the gel points in both OL simulation and FS theory. In contrast, the D...