Grand canonical Monte Carlo simulation and simple statistical thermodynamic theory are used to model the aggregation and phase separation of systems of reversibly polymerizing monomers, capable of forming chains with or without the ability to cyclize into rings, with isotropic square-well attractions between nonbonded pairs of monomers. The general trend observed in simulation of chain-only systems, as predicted in a number of published theoretical works, is that the critical temperature for phase separation increases and the critical monomer density decreases with rising polymer bond strength. Introduction of the equilibrium between chains and rings into the theory lowers the predicted critical temperature and increases the predicted critical density. While the chain-only theories predict a vanishing critical density in the limit of complete polymerization, when ring formation is taken into account the predicted critical density in the same limit approaches the density of the onset of the ring-chain transition. The theoretically predicted effect of cyclization on chemical potential is in good qualitative agreement with a subset of simulation results in which chain-only systems were compared with equilibrium mixtures of rings and chains. The influence of attractions on the aggregation number and radius of gyration of chains and rings observed in simulations is also discussed. (c) 2007 American Institute of Physics.
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