Phase Behavior of a Mixture of Poly(isoprene)−Poly(oxyethylene) Diblock Copolymer and Poly(oxyethylene) Surfactant in Water

The phase behavior of a mixture of poly(isoprene)−poly(oxyethylene) diblock copolymer (PI−PEO or C250EO70) and poly(oxyethylene) surfactant (C12EO3, C12EO5, C12EO6, C12EO7, and C12EO9) in water was investigated by phase study, small-angle X-ray scattering, and dynamic light scattering (DLS). The copolymer is not soluble in surfactant micellar cubic (I1), hexagonal (H1), and lamellar (Lα) liquid crystals, whereas an isotropic copolymer fluid phase coexists with these liquid crystals. Although the PI−PEO is relatively lipophilic, it increases the cloud temperatures of C12EO3 - 9 aqueous solutions at a relatively high PI−PEO content in the mixture. Most probably, in the copolymer-rich region, PI−PEO and C12EO n form a spherical composite micelle in which surfactant molecules are located at the interface and the PI chains form an oil pool inside. In the C12EO5/ and C12EO6/PI−PEO systems, one kind of micelles is produced in the wide range of mixing fraction, although macroscopic phase separation was observed within a few days after the sample preparation. On the other hand, small surfactant micelles coexist with copolymer giant micelles in C12EO7/ and C12EO9/PI−PEO aqueous solutions in the surfactant-rich region. The micellar shape and size are calculated using simple geometrical relations and compared with DLS data. Consequently, a large PI−PEO molecule is not soluble in surfactant bilayers (Lα phase), infinitely long rod micelles (H1 phase), and spherical micelles (I1 phase or hydrophilic spherical micelles) as a result of the packing constraint of the large PI chain. However, the copolymer is soluble in surfactant rod micelles (C12EO5 and C12EO6) because a rod−sphere transition of the surfactant micelles takes place and the long PI chains are incorporated inside the large spherical micelles.