Association Properties of Diblock Copolymers of Propylene Oxide and Ethylene Oxide in Aqueous Solution. The Effect of P and E Block Lengths

Three diblock copolymers of propylene oxide and ethylene oxide were prepared by sequential oxyanionic polymerization; P 94 E 316, P 60 E 348, and P 43 E 312 . Light scattering and dye solubilization were used to confirm micellization in dilute aqueous solution and to determine the temperature dependence of the critical micelle concentration (cmc), and eluent gel permeation chromatography was used to determine the extent of micellization. Comparison with results for the series of copolymers E m P n ( m = 98−104, n = 37−73, published previously) shows that values of the cmc in molar units depend almost entirely on P-block length, i.e., that the effect of E-block length on critical micelle concentration is insignificant in the range m = 100−300. Light scattering was also used to determine micellar association numbers ( N w ) and radii. Present and previous values of N w fit well to a scaling law for block lengths (P and E) similar to that proposed by Nagarajan and Ganesh for E m P n copolymers. Gel boundaries were determined by a tube-inversion method, and critical gel concentrations were found to coincide with values predicted by using micellar parameters determined by static light scattering.