Off-Lattice Monte Carlo Simulation of Hyperbranched Polymers, 2. Effect of the Reactivity Ratio of Linear to Terminal Unit on the Microstructure of Hyperbranched Polymers Based on AB2 Monomers

Abstract

The polycondensation of hyperbranched polymers was simulated using an off‐lattice Monte Carlo method in order to investigate the effect of reactivity ratio (x) of linear to terminal unit on the microstructure of hyperbranched polymers based on AB2 type monomers. The polydispersity index (PI) shows a maximum when the reactivity ratio is 1.0 and decreases as the reactivity ratio deviates from unity. Fractions of dendritic, linear and terminal units were determined from simulation and compared with theoretical predictions. As the reactivity ratio increases, the formation of the dendritic unit is more favored. The relative Wiener indices, free from the polydispersity effects, were newly defined in this simulation. The relative Wiener indices increases with increasing the reactivity ratio, indicating that the more branched structures are formed as the reactivity ratio increases.

Predicting multidimensional distributive properties of hyperbranched polymer resulting from AB2 polymerization with substitution, cyclization and shielding

“…In previous work, scalar quantities like average molecular weight, polydispersity, degree of branching, or gel point have been successfully predicted. These results were mainly achieved either by statistical theories of Stockmayer [1,2] and Flory [3] or, later, by stochastic simulations [4] and a generating functions approach [5,6,7]. Most theoretical models that describe the polymerization of AB 2 monomer are based on the assumption that all functional groups of the same type are equally reactive, and react independently of one another.…”