Synthesis and characterization of PEO-PCL-PEO triblock copolymers:: Effects of the PCL chain length on the physical property of W1/O/W2 multiple emulsions

A series of poly(ethylene glycol)-block-poly(epsilon-caprolactone)-block-poly(ethylene glycol) (PEO-PCL-PEO) triblock copolymers were prepared and then used for the investigation of the effects of the ratio of epsilon-caprolactone to poly(ethylene glycol) (i.e., [CL]/[EO]) on the physical properties of water-in-oil-in-water (W-1/O/W-2) multiple emulsions containing a model reagent, ascorbic acid-2-glucoside (AA2G). In the synthesis, the [[CL]/[EO] was varied from 0.11 to 0.31. The molecular weights and compositions of PEO-PCL-PEO were determined by GPC and H-1 NMR analyses. Thermal behavior and crystal formation were studied by DSC, XRD, FT-IR, and polarized optical microscopy (POM). Aggregate behavior of PEO-PCL-PEO was confirmed by DLS, UV, and H-1 NMR. Morphology and relative stiffness of the W-1/O/W-2 multiple emulsions in the presence of PEO-PCL-PEO were studied by confocal laser scanning microscopy (CLSM) and rheometer. Variation in the [CL]/[EO] significantly affects the crystalline temperature and spherulite morphology of PEO-PCL-PEO. As the [CL]/[EO] increases, the CMCs of PEO-PCL-PEO decreases and the slope of aggregate size reduction against the copolymer concentration becomes steeper except for the lowest [CL]/[EO] value of PEO-PCL-PEO (i.e., P-222). P-222 significantly increases the viscosity of continuous (W-2) phase, which implies the copolymer would exist in the W2 phase. On the other hand, the triblock copolymers with relatively high [CL]/[EO] ratios mainly contribute to the size reduction of multiple emulsions and the formation of a firm wall structure. The particle size of the multiple emulsion decreases and the elastic modulus increased as [CL]/[EO] increases, confirmed by microscopic and rheometric analyses. (C) 2008 Elsevier B.V. All rights reserved.