4.7 Article

Polymer EVA-OH membrane with improved water/gas separation performance: Influence of VAc/VOH repeating units ratio on membrane physical chemical properties

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JOURNAL OF MEMBRANE SCIENCE
卷 673, 期 -, 页码 -

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ELSEVIER
DOI: 10.1016/j.memsci.2023.121386

关键词

EVA; Partial hydrolysis; 1D and 2D NMR analysis; Polymer membrane; Water; gas separation; Membrane selectivity

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New hydrolyzed EVA-OH membranes were synthesized for water/gas separation. The reaction conditions were optimized to achieve desired chemical structure. The change in EVA-OH composition significantly influenced membrane crystallinity.
New hydrolyzed ethylene vinyl acetate (EVA) (EVA-OH) membranes were synthesized via the EVA partial hydrolysis reaction for the use in the water/gas separation field. The reaction conditions of the partial hydrolysis were optimized in terms of the EVA-OH chemical structure by using 1D and 2D NMR spectroscopy. It has been shown that a change of the EVA-OH chemical composition (i.e. the ratio between vinyl alcohol (VOH) and vinyl acetate (VAc) repeating units) has a significant influence on the membrane crystallinity due to a different nature of the VOH and VAc repeating units. The VAc groups act as a soft (i.e. amorphous) segmental unit owing to the low organization of the polymer chains, whereas the VOH groups operate as a rigid (i.e. semi-crystalline) unit because of the formation of the VOH crystals via the interchain interactions (i.e. hydrogen bonding between free alcohol groups). Thus, the noticeable change of the EVA-OH glass transition temperature Tg is observed depending on the hydrolysis degree - the Tg value of the EVA-OH 1 membrane (i.e. with 44 wt% of VAc) is -9 degrees C, while for the EVA-OH 5 membrane (i.e. with 9 wt% of VAc) it equals to - 19 degrees C. Such a change of the membrane morphology allowed us to optimize the mechanical and transport properties of EVA-OH membranes. The presence of the rigid VOH repeating units positively influences the membrane tensile stiffness and resistance, thereby preventing the membrane adhesive properties. Consequently, the EVA-OH membrane tensile stiffness, stress at break, and elongation are varied in the range of 2.5-204 MPa, 4-45 MPa, and 1450-600%, respectively, depending on the VOH content. Besides, the amorphous VAc segmental units generate a higher permeation flux (i.e. higher water/gas permeability), whereas the semi-crystalline VOH repeating units ensure the membrane barrier properties and improve its selectivity. In addition, EVA-OH polymer membranes demonstrate a promising CO2 separation performance in terms of the gas selectivity. The best EVA-OH membrane shows the selectivity coefficient alpha(CO2/N2) of - 75 and alpha(CO2/O2) of - 13.

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