Synthesis and rheological behavior of hydrophobically modified block copolymers

Hydrophobically modified polymers were synthesized via esterification reactions between a commercial triblock copolymer composed of ethylene oxide (EO) and propylene oxide (PO) segments (EO20PO70EO20) and lauric and oleic acids. Rheological studies of aqueous systems containing the original copolymer and the synthesized products were performed to evaluate the effects of chemical modification, the presence of salt, and temperature on the rheology of the systems due to changes in the micellar structures. It was verified that the systems containing the synthesized products presented shear-thinning behavior even in the absence of salt. In addition, increasing the temperature and salt concentration enhanced the hydrophobic character of the poly(propylene oxide) segment and reduced the hydration of the poly(ethylene oxide) segment; this favored the adequate packing needed to form long, wormlike micelles and resulted in pronounced shear thinning. The formation of a complex micelle structure probably occurred in the systems above the critical micellar temperature of the original copolymer because under this condition the molecules presented three alternate hydrophobic segments that had to dive into the micelle structure. The formation of long, wormlike micelles was also evidenced by the Maxwellian behavior observed in rheological oscillatory measurements. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010