We study the dynamics of collapse of a polysoap by means of large-scale molecular dynamics simulation and scaling arguments. A polysoap consists of a hydrophilic backbone and hydrophobic side chains attached at regular intervals along the backbone. In selective solvent conditions, the hydrophobic components aggregate, forcing the hydrophilic backbone to form loops anchored at the surface of the core, ultimately forming a micelle. The kinetics of polysoap collapse includes two major mechanisms: (1) early aggregation of the hydrophobic side chains controlled by first-order kinetics whose rate constant is given by a contact probability and (2) coalescence into larger clusters which requires activation to overcome energy barriers due to excluded volume repulsions between intermediate micelle coronas. In the late stage, the energy barrier is increasing as p3/2, with p the number of aggregated side chains in an intermediate micelle. The corresponding late-stage rate constant decays exponentially as exp(−p3/2).

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