High-Pressure Micellar Solutions of Symmetric and Asymmetric Styrene–Diene Diblocks in Compressible near Critical Solvents: MP and CP Respond but MCP Insensitive to Copolymer Molecular Weight, Concentration, and Block Ratio Changes

High-pressure solutions of styrene–diene copolymers in compressible solvents, such as polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane or propylene, exhibit a robust micellar region that grows in pressure–temperature coordinates with increasing copolymer concentration, molecular weight, and styrene/diene block ratio. This happens because, while the micellization pressure strongly increases with increasing copolymer concentration, molecular weight, and styrene/diene block ratio, the micellar cloud pressure (the pressure at which the micelles aggregate and precipitate from solution) is largely insensitive to these variables. In other words, neither the block size nor the block ratio nor the copolymer concentration seems to affect much the copolymer separation from solution in the micellar region.