Water-soluble hyperbranched polyester (WHBP) was synthesized through the esterification reaction of the fourth generation hyperbranched polyester and maleic anhydride. A novel cross-linked WHBP/PVA membrane was prepared by adding WHBP into poly(vinyl alcohol) (PVA) solution with glutaraldehyde as the cross-linker. WHBP was characterized by Nuclear Magnetic Resonance and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), while WHBP/PVA membranes were characterized by ATR-FTIR, X-ray Diffraction, Scanning Electron Microscopy, Thermogravimetric Analysis, mechanical capacity, and water contact angle. Testing results showed that maleic anhydride was grafted on the surface of WHBP; compared with PVA membrane, WHBP/PVA membrane had lower crystallinity, weaker mechanical strength, higher hydrophilicity, and better thermal stability. Sorption and diffusion behaviors of n-butanol and water in WHBP/PVA membrane were investigated; pervaporation performances of WHBP/PVA membrane were studied through the dehydration of the 90 wt % n-butanol aqueous solution at 40 8C. With an increase of the WHBP content from 0 to 30 wt %, both n-butanol uptake and n-butanol diffusion coefficient first decreased then increased; n-butanol flux first decreased from 10 to 2 gÁm
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