Off-Lattice Simulation of Multifunctional Monomer Polymerizations:Effects of Monomer Mobility,Structure,and Functionality on Structural Evolution at Low Conversion

摘要

Fundamental insight into the polymerization behavior and structural evolution of highly cross-linked polymers synthesized from the chain polymerization of multifunctional monomers will benefit a number of current and emerging applications.This contribution reintroduces' an off-lattice kinetic gelation model with refinements to the representations of monomer mobility,structure,and functionality,which more realistically capture low conversion propagation events during cross-linked network evolution.Intramolecularly cross-linked macro-molecules (ICMs) are formed by simulation of a single propagating radical within a volume containing ca.100 000 monomer units.Effects of monomer mobility,structure,and functionality on the relative size,kinetic chain length,and intramolecular cross-link density of ICMs are reported.Finally,aspects of percolation theory are applied to this off-lattice kinetic gelation simulation.The fractal dimension corresponds to the theoretical value for a lattice animal created by a three-dimensional percolation model and it is independent of conversion.Overall,this contribution demonstrates the utility of a unique approach for kinetic gelation simulation of multifunctional monomer polymerizations that affords more realistic representation of monomer structure and dynamics than traditional,lattice-based models.