Self-assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small-angle x-ray scattering

摘要

The aggregation behaviour of styrene-vinyl benzoic acid (PSm-b-PVBAn) amphiphilic diblock copolymers inselective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We havecarried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymersof narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found thatthe aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms flat disc objectswith the ratio of radius w=0.4. The average radius gyration Rg of the copolymer decreases as solvents change fromisopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with theaddition of CoCl2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h) ∞ h-α indifferont selective solutions, suggesting that the PSm-b-PVBAn coils have self-similar structure behaviour or a fractalstructure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changesdramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (Dm) from2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course ofchanging solvents, decreasing surface fractal dimension (Ds) from 2.98 to 2.58 indicates that the copolymer micellechange from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasingDm and Ds from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rathercompact and rough disc form by adding CoCl2 in ethanol solvents.