Theory of the Flower Micelle Formation of Amphiphilic Random and Periodic Copolymers in Solution.

The mixing Gibbs energy Δgm for the flower-micelle phase of amphiphilic random and periodic (including alternating) copolymers was formulated on the basis of the lattice model. The formulated Δgm predicts (1) the inverse proportionality of the aggregation number to the degree of polymerization of the copolymer, (2) the increase of the critical micelle concentration with decreasing the hydrophobe content, and (3) the crossover from the micellization to the liquid⁻liquid phase separation as the hydrophobe content increases. The transition from the uni-core flower micelle to the multi-core flower necklace as the degree of polymerization increases was also implicitly indicated by the theory. These theoretical results were compared with experimental results for amphiphilic random and alternating copolymers reported so far.