The effect of PEG-content and molecular weight of PEG-PPG-PEG block copolymers on the structure and performance of polyphenylsulfone ultra- and nanofiltration membranes

Thin-film composite (TFC) membranes obtained by forming a selective polyamide (PA) layer on a surface of a porous membrane-substrate via interfacial polymerization (IP) technique are the most effective membranes for nanofiltration (NF). The idea of this study is that addition of polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) block copolymers to the polyphenylsulfone (PPSU) casting solution tunes the pore structure (pore size and porosity), water contact angle and topology of the selective layer of ultrafiltration (UF) membranes. This influences the formation of PA layer via IP since membrane-substrate significantly effects the first stage of IP reaction. For the first time the effect of PEG-PPG-PEG copolymer molecular weight, content of PEG blocks and copolymer concentration in the PPSU casting solution on the structure, hydrophilicity and performance of ultrafiltration and TFC NF membranes was revealed. It was found that increase in PEG block content and PEG-PPG-PEG molecular weight led to the increase in pore size, porosity and hydrophilicity of selective layer of ultrafiltration membranes which results in the formation of thinner and more uniform PA layer with higher cross-linking degree of NF membranes via IP. It was revealed that NF membrane flux increased with the rise in the content of PEG units from 10 to 80 wt.% and increase in molecular weight of PEG-PPG-PEG block copolymer. Modification of PPSU membrane-substrate yielded the increase in selectivity of the corresponding TFC NF membranes due to the formation of more uniform and denser defect-free PA layer attributed to the rise in hydrophilicity of membrane substrate. It was found that membrane substrate modification by PEG-PPG-PEG results in the enhancement of antifouling performance toward bovine serum albumin (flux recovery ratio is 99-100%) and long-term stability during 48 h operation compared to the reference membrane. Modification of PPSU membrane substrate by F38 PEG-PPG-PEG block copolymer (Mn= 5 000 g·mol-1, PEG block content of 80 wt.%) was found to yield the TFC NF membranes with the best combination of permeation, separation and antifouling performance and long-term stability.