This study deals with the investigation of the phase state of the polymer systems from polysulfone (PSF) with the addition of polyethylene glycol (PEG-400, Mn = 400 g·mol−1) and polyvinylpyrrolidone (PVP K-30, Mn = 40,000 g·mol−1) in N,N-dimethylacetamide (DMA), which feature lower critical solution temperatures (LCSTs). A fragment of the phase state diagram of the system PSF —PEG-400—PVP K-30—DMA was experimentally constructed in the following range of component concentrations: PSF 20–24 wt.%, PEG-400—35–38 wt.% and PVP—0–8 wt.%. It has been established that PVP addition substantially reduces the phase separation temperature down to 50–60 °C. Based on the obtained phase diagrams, a method for preparation of highly permeable hollow fiber membranes from PSF, which involves the processing of the dope solution at a temperature close to the LCST and the temperature of the bore fluid above the LCST, was proposed. Hollow fiber membranes with pure water flux of 1200 L·m−2·h−1 and a sponge-like macrovoid-free structure were obtained via LCST-thermally induced phase separation by free fall spinning technique.
