Critical micelle concentrations of block and gradient copolymers in homopolymer: Effects of sequence distribution,composition, and molecular weight

The critical micelle concentrations (CMCs) of styrene–methyl methacrylate (S-MMA) block and gradient copolymers present in a homopolymer poly(methyl methacrylate) (PMMA) matrix were determined using an intrinsic fluorescence technique based on the ratio of excimer to monomer fluorescence from styrene repeat units. The homopolymer molecular weight (MW) and copolymer MW, composition, and sequence distribution were varied to determine their effects on the CMC, and comparisons were made to theory. Although the effects of these parameters on micelle formation have been the focus of significant theoretical study, few experimental studies have addressed these issues. The MW of the S block (forming the micelle core) has a strong effect on the CMC. For example, an order of magnitude reduction in the CMC (from ∼ 1 to ∼ 0.1 wt %) is observed when the S block MW is increased from 51 to 147 kg/mol while maintaining the MMA block and PMMA MWs at 48–55 kg/mol. Increasing the PMMA matrix MW also has a strong an effect on the CMC, with the CMC for a nearly symmetric S-MMA block copolymer with each block MW equal to 48–51 kg/mol decreasing by a factor of 5 and by several orders of magnitude when the matrix MW is increased from 55 to 106 kg/mol and 255 kg/mol, respectively. In contrast, similar changes in the MMA block MW have little effect on the CMC. Finally, when present in a 55 kg/mol PMMA matrix, a 55 kg/mol S-MMA gradient copolymer with a styrene mole fraction of 0.51 exhibits a factor of 6 larger CMC than a block copolymer of similar MW and composition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2672–2682, 2008