Self-assembly and crystallization behavior of a double-crystalline polyethylene-block-poly(ethylene oxide) diblock copolymer

The self-assembly and crystallization behavior of a well-defined low molecular weight polyethylene-block-poly(ethylene oxide) (PE-b-PEO) diblock copolymer was studied. The number-average degrees of polymerization for the PE and PEO blocks were 29 and 20, respectively. The molecular weight distribution was 1.04 as determined by size-exclusion chromatography. The PE-b-PEO sample exhibited two melting points at 28.7 and 97.4 °C for the PEO and the PE crystals, respectively. The crystallization of the PE blocks was unconfined, while the crystallization of the PEO blocks was confined between pre-existing PE crystalline lamellae, as demonstrated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) studies. In the fully crystalline state, both PE and PEO blocks formed extended-chain crystals with PE chains tilted ∼22° from the lamellar normal and PEO chains parallel to the lamellar normal, as evidenced by two-dimensional WAXD study of shear-oriented samples. Regardless of hydrogen bonding among hydroxyl chain ends in the PEO blocks, interdigitated, single-crystalline layer morphology was observed for both PE and PEO crystals. The partial crystalline morphology, where the PE crystallizes and the PEO is amorphous, had the same overall d-spacing as the fully crystalline morphology. A double-amorphous PEO layer sandwiched between neighboring PE crystalline layers was deduced based on a chain conformation study using Fourier transform infrared. The confined crystallization kinetics for PEO blocks was investigated by differential scanning calorimetry, which could be explained by a heterogeneous nucleation mechanism. The slower crystallization rate in the PEO-block than the same molecular weight homopolymer was attributed to the effects of nanoconfinement and PEO chains tethered to the PE crystals.