Coincident or sequential crystallization of PCL and PEO blocks within polystyrene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) linear triblock copolymers

In this work, the behavior of the crystallizable blocks within polystyrene-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone) linear triblock copolymers is studied. The apparent crystallization and melting temperatures of PEO and PCL can be coincident as a result of their close values, their dependence on the molecular weight of the blocks and on the relative amount of each component within the copolymers. When the content of both PEO and PCL is low, typically 20% or less, both blocks crystallized coincidentally upon cooling from the melt at very large supercoolings (T-c = -40 degreesC), suggesting that homogeneous nucleation has taken place. A S63EO16C20 copolymer (where subscripts denote the weight fraction of the components) exhibited a small angle X-ray scattering (SAXS) pattern at room temperature that suggests a cylindrical morphology for the minor components, where the crystallization of PEO and PCL blocks can take place subsequently near -40 degreesC in a hard confinement fashion within the vitreous PS matrix. We have employed differential scanning calorimetry (DSC) to study the self-nucleation process and the results indicate that the difficulty in generating enough self-seeds to nucleate every isolated microdomain causes the disappearance of Domain If (or exclusive self-nucleation Domain) and therefore a direct transition from complete melting (Domain 1) to self-nucleation and annealing (Domain III) is observed. When the content of both PEO and PCL blocks is larger than 35%, a coincident crystallization can be observed as well as coincident melting. For a S15EO37C48 triblock copolymer, PS is a minor phase and mixed spherulites composed of both PCL and PEO blocks were observed by Polarized Optical Microscope (POM) at appropriate supercoolings. In this case, the self-nucleation behavior is standard, and through its use the crystallization and melting process of both blocks can be separated. Wide angle X-ray scattering (WAXS) at different temperatures was used to corroborate the sequential melting of both semicrystalline blocks deduced by self-nucleation. Isothermal crystallizations were also followed by WAXS as a function of time and the results showed that depending on the crystallization temperature (T-c), only the PCL block crystallizes (at high T-c), or the PCL block crystallizes first followed by the PEO at later times (at lower T-c). (C) 2004 Elsevier Ltd. All rights reserved.