Monte Carlo Simulation Of Living Polymerization And Polymerization-Induced Copolymers Self-assembly

The amphiphilic copolymers with narrow molecular weight distribution could self-assemble into a variety of micelles and vesicles. These aggregates have potential applications in various fields, such as in biomedicine, catalysis, microelectronics, etc. In order to obtain a regular structure with uniform size distribution, the molecular weight distribution and composition of the copolymers must be well controlled. Liv-ing ionic polymerization and controlled/living radical polymerization are known to fabricate polymers with narrow molecular weight distribution. Being different with the self-assembly of copolymers, polymerization induced self-assembly is a simple and feasible approach to prepare materials with nanostructures.In this thesis, we study the self-assembly of copolymer in solution using Monte Carlo simulation of "single-site bond fluctuation" model and "eight-site bond fluctua-tion" model. A new Monte Carlo simulation schedule is developed based on "sin-gle-site bond fluctuation" model to study the kinetics of living radical polymerization. In the process of polymerization, we studied the polymerization induced self-assembly and observed spherical and cylindrical micelles in solution. Our simula-tion confirmed the polymerization induced self-assembly observed in experiments, and revealed the underlined dynamic process of it.1. We used Monte Carlo computer simulation based on both "single-site bond fluc-tuation" model and "eight-site bond fluctuation" model to study self-assembly of the block copolymers in solution. Specifically, we investigate the variation of self-assembled morphologies of the diblock copolymers depending on the system parameters such as:concentration, the length of the corona-forming blocks and core-forming blocks and the repulsive interaction between the corona-forming block and the solvent. We found that, the "eight-site bond fluctuation" model is more efficient than "single-site bond fluctuation" while the morphologies found by "single-site bond fluctuation" model are richer.2. We applied both "single-site bond fluctuation" model and "eight-site bond flue- tuation" model Monte Carlo simulation to study the kinetics process of living radical polymerization. The kinetic process has been proved to be a living polym-erization by investigating monomer conversion, molecular weight and molecular distribution et al. The results show that increasing the probability of termination, the number of "living" polymers and their lifetime could increase the polydisper-sity index. The "single-site bond fluctuation" model established on the basis of the previous eight-site model could be used to study the controlled living radical po-lymerization reaction.3. The "single-site bond fluctuation" model and "eight-site bond fluctuation" model Monte Carlo simulation are used to study the polymerization induced copolymers self-assembly in solution. We investigate the influence of probability of reaction, the rate of annealing and the interaction between the blocks and the solvent on the morphologies. Our simulation confirmed the polymerization induced self-assem-bly observed in experiments, and revealed the underlined dynamic process of it. This study testified that, the Monte Carlo simulation schedule is apt to study the phase behavior of polymerization induced self-assembly.