Effects of a PPO-PEO-PPO triblock copolymer on micellization and gelation of a PEO-PPO-PEO triblock copolymer in aqueous solution

The effects of a PPO-PEO-PPO triblock copolymer (25R4, PO,(19)-EO33-PO19) on thermoreversible micellization and gelation properties of a PEO-PPO-PEO triblock copolymer (F108, EO133-PO50-EO133) in water were studied by means of micro-DSC and rheology. A complete, mirror-image like thermoreversible behavior has been observed for all of the samples with various molar ratios of 25R4 to F108. At a given concentration of F 108, the addition of 25R4 results in the salt-out like effect on the primary micellization of F108; that is, the critical micellization temperature (CMT) of F108 shifts to lower temperatures with increasing the content of 25R4. The enthalpy changes for micellization are a linear function of the 25R4/F108 molar ratio at a fixed F108 concentration. Beyond the primary peak for the micellization of F108, a secondary peak or shoulder is observed in the DSC curves for the samples with the higher 25R4/F108 molar ratios, due to the formation of the hydrophobic aggregates from both the PPO blocks of F108 and those (i.e., PPO blocks) of 25R4. Furthermore, as an example, the dynamic viscoelastic properties of 18 wt % F108 solutions with various contents of 25R4 have been examined. It is found that, when the 25R4/ F108 molar ratio <= 1, 25R4 does not affect the gelation of F108 notably. When the ratio is greater than 1, however, the formation of the 25R4-bridged micellar aggregates delays the gelation of F108 significantly. A schematic model has been proposed to explain the mechanism for the 25R4-influenced micellization and gelation of F108.