Self-association of block copoly(oxyalkylene)s in aqueous solution. Effects of composition, block length and block architecture.

The article deals with the association behaviour in dilute aqueous solution of block copoly(oxyalkylene)s in which hydrophilic poly(ethylene oxide) is combined with hydrophobic poly(propylene oxide), poly(1,2-butylene oxide) or poly(styrene oxide). Polymers with three simple architectures are considered, i.e. copolymers of type EmAn, EmAnEm and AnEmAn, where E denotes an oxyethylene unit, A denotes a hydrophobic oxyalkylene unit, and the subscripts m and n denote number-average block lengths in repeat units. The aim is to examine how composition, block length and block architecture govern two fundamental properties, critical micelle concentration (cmc) and micelle association number (N), for systems which are in dynamic equilibrium. Copolymers with properties known to be greatly affected by heterogeneity in composition are excluded from consideration. A uniform pattern of behaviour emerges when log(cmc) is plotted against reduced hydrophobic block length (x), consistent with the micellisation equilibrium changing from one between unimers and multimolecular micelles at low values of x, to one between unimolecular micelles and multimolecular micelles at high values of x. Support for this model is provided by the enthalpy of micellisation, values of which fall effectively to zero as x is increased. Values of the micelle association number are used to define a critical hydrophobic block length for micellisation (n(cr)) for each class of diblock copolymers, values of which apply equally well to the half-length of the central block of corresponding EmAnEm triblock copolymers. Given these values, and irrespective of block architecture, the overall scaling law for the weight-average association number of the micelles is shown to be Nw = n'(1.07)m(-0.63) where m is the length (or half-length) of the hydrophilic block, and n' is the effective length of the hydrophobic block, equal to its length (or half-length) minus the critical length, i.e. n' = n-n(cr).