Off‐lattice Monte Carlo simulation of hyperbranched polymers, 1 Polycondensation of AB2 type monomers

The polycondensation of hyperbranched polymers, based on AB₂ type monomers, was simulated using an off‐lattice Monte Carlo method in order to investigate the polymerization kinetics and microstructures of hyperbranched polymers. The effects of temperature and activation energy of reaction on the conversion rate seem qualitatively acceptable, indicating that our simulation model properly describes the polymerization reaction of hyperbranched polymers. Number average degree of polymerization and polydispersity index were calculated as a function of conversion and compared with Flory's expectation. Fractions of dendritic, linear and terminal unit were also determined from simulation and compared with theoretical predictions. As the hyperbranched polymer grows, it is observed that the molecular shape changes from a regular fan‐shape structure to an edge‐curled up structure.