Abstract
We have used pyrene fluorescence spectroscopy and isothermal titration calorimetry (ITC) to investigate the effect of hydrophobic-block length on values of the critical micelle concentration (cmc) for aqueous solutions of triblock poly(butylene oxide)–poly(ethylene oxide)–poly(butylene oxide) block copolymers (BnEmBn, where m and n denote the respective block lengths) with hydrophobic block lengths in the range n=12–21. Combined with results from previous work on BnEmBn copolymers with shorter B blocks, plots of log10(cmc) (cmc in molar units and reduced to a common E-block length) against total number of B units (nt=n for diblock or nt=2n for triblock copolymers) display transitions in the slopes of the two plots, which indicate changes in the micellisation equilibrium. These occur at values of ntwhich can be assigned to the onset and completion of collapse of the hydrophobic B blocks, an effect not previously observed for reverse triblock copolymers. The results are compared with related data for diblock EmBn copolymers.
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