Micellization and gelation of triblock copolymers of ethylene oxide and styrene oxide in aqueous solution

Nine triblock copolymers of ethylene oxide and styrene oxide (type EmSnEm, E = oxyethylene, S = oxyphenylethylene, n and m = number-average block lengths) were prepared by sequential oxyanionic polymerization. Surface tensiometry was used to determine critical micelle concentrations (cmc's) and standard enthalpies of micellization, and isothermal titration calorimetry was used to confirm the enthalpy of micellization. Light scattering was used to determine micellar association numbers and hydrodynamic radii. Phase diagrams defining regions of hard and soft gel were determined by tube inversion and Couette rheometry. Comparison is made with reported results for diblock copolymers of ethylene oxide and styrene oxide and, so far as possible, with results for triblock copolymers of ethylene oxide and styrene. Compilation of values of the cmc for three series of triblock copoly(oxyalkylene)s, EmSnEm, EmBnEm (B = oxybutylene), and EmPnEm (P = oxypropylene), reveals a discontinuity in the block length dependence of log(cmc) at S-6 and B-12.