Mixed block copolymer aggregates with tunable temperature behavior.

A block copolymer of propylene oxide (PO) and ethoxyethyl glycidyl ether (EEGE), (PO)(2)(EEGE)(6)(PO)(2), that has been found to possess lower critical solution temperature properties in water in the temperature range below 20 degrees C was mixed at 1:0.1, 1:1, and 1:10 weight ratios with commercially available Pluronic (L64 or P85) block copolymers. The cooperative association of the copolymers in aqueous solution was studied by dynamic light scattering over a wide temperature range (5-60 degrees C). At lower temperatures, the systems containing either L64 or P85 behave similarly irrespective of the composition: three species corresponding to (PO)(2)(EEGE)(6)(PO)(2) unimers, Pluronic-dominated mixed micelles, and large (50-60 nm in radius) composite (PO)(2)(EEGE)(6)(PO)(2)/Pluronic aggregates were identified. At a certain temperature, which is composition-dependent, the systems phase-separate [(PO)(2)(EEGE)(6)(PO)(2)/L64 1:0.1], enter an interval of instability [(PO)(2)(EEGE)(6)(PO)(2)/L64 1:1 and 1:10], or rearrange by dissociation of the large composite particles [(PO)(2)(EEGE)(6)(PO)(2)/P85]. The presence of a Pluronic micellar peak in the relaxation time distribution at lower temperatures, the dimensions of the composite particles, and the different behavior of the systems at elevated temperatures are discussed. A possible application of the thermosensitive mixtures in delivery/release of active substances is suggested.