Elsevier

Applied Surface Science

Volume 483, 31 July 2019, Pages 278-284
Applied Surface Science

Full length article
Preparation and characterization of acid and solvent resistant polyimide ultrafiltration membrane

https://doi.org/10.1016/j.apsusc.2019.03.226Get rights and content

Highlights

  • A novel polyimide polymer was synthesized by a two-step method using TMPDA, MDA and BTDA.

  • The polyimide ultrafiltration membrane with fully developed finger-like macro voids were prepared by phase inversion.

  • The PI membrane displayed a satisfactory water flux recovery ratio of 90.03% in the recovery experiments.

  • The PI membrane can operate stably in 1 mol L-1 hydrochloric acid solution and the retention rate of BSA remains at 93%.

  • The flux of the PI membrane is 325.60 L m-2h-1 and the BSA retention rate is still higher than 95% after soaking in various solvents for 7 days.

Abstract

In this study, a new type of polyimide (PI) composite material was synthesized by a two-step method using 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPDA), 4,4′-methylenedianiline (MDA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA). The PI material was then used to prepare an ultrafiltration (UF) membrane by phase inversion method. The membrane showed a dense surface layer, a porous sublayer, and fully developed finger-like macrovoids at the bottom, which had excellent hydrophilicity and antifouling property. In the recovery experiments with a protein solution, the PI membrane displayed a satisfactory water flux recovery ratio of 90.03%. The PI membrane can operate stably in 1 mol L−1 hydrochloric acid solution, and the retention rate of BSA remains at 93%. In addition, the flux of the membrane is 325.60 L m−2 h−1 and the BSA retention rate the retention rate is still higher than 95% after soaking in various solvents for 7 days.

Introduction

Over the past decades, ultrafiltration has received considerable attention, and it has been widely used in many fields including water purification [1], protein concentration [2,3], and reverse osmosis pretreatment [4]. However, its numerous applications are adversely impacted by fouling from proteins and corrosion from harsh conditions, such as solutions with organic solvents or strong pH [[5], [6], [7]].

The membrane material is a decisive factor in determining the various properties of membranes, such as hydrophilicity, morphology, surface charge, and allowable pH value [[8], [9], [10]]. All these properties have a direct influence on the membrane performance including permeability and selectivity [[11], [12], [13], [14], [15]]. High-performance polymers such as polysulfone, polyphenylenesulfide (PPS), polybenzimidazole (PBI) and polyethersulfone are widely used for organic solvent nanofiltration [[16], [17], [18], [19]]. Ignacz et al. fabricated Polymer blend membranes, for solvent-resistant nanofiltration in polar aprotic solvents by ion-stabilization methodology [20]. However, they require a stable crosslinking or ion-stabilization to achieve the desired solvent resistance [21,22].

Polyimides (PI) satisfy a number of key requirements for an ideal membrane material, such as excellent heat resistance, chemical resistance, dimensional stability, mechanical properties, and good membrane-forming properties [[22], [23], [24], [25], [26]]. Huang et al. developed novel GO/PI hollow fiber membranes for seawater desalination which is promising for desalination of seawater and brackish water attributing to the hydrophilic properties as well as the high stability in seawater [27]. Liu et al. prepared a novel z-pi film by immersion precipitation methodwhich processed several advantages such as high hydrophilic, high water permeation property, excellent fouling resistant ability and performance stability [28]. However, current studies on PI ultrafiltration membranes are limited for improving the throughput and antipollution capabilities, and development of zwitterion membrane materials. Moreover, few studies have tested PI membranes under extreme conditions such as high temperature and strong acid [1,[29], [30], [31], [32]].

In this study, we first prepared a PI polymer material with the desired microstructure, which was then used to prepare an ultrafiltration membrane. Then, we characterized the structure and thermal properties of the PI and evaluated the surface properties and selective permeability of the membranes.

Section snippets

PI synthesis

PI was synthesized from 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPDA), 4,4′-methylenedianiline (MDA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) using a conventional two-step method through a chemical imidization reaction, as shown in Fig. 1. The typical procedure is as follows: In a clean and dry 100-mL three-neck round-bottom flask, 0.821 g (5 mmol) of TMPDA, 0.991 g (5 mmol) of MDA, and 50 mL of N-methyl pyrrolidone (NMP) were taken. The reaction mixture was stirred at

Characterization of the polymer structure

The FTIR spectrum of PI is shown in Fig. 2. The characteristic major absorption bands of imide ring were observed at 1776 cm−1 (asymmetric stretching of the carbonyl group of imide ring), 1728 cm−1 (asymmetric stretching of the carbonyl group of imide ring), and 1368 cm−1 (C–N bond of imide ring). In addition, characteristic major absorption bands of the carbonyl group attached to the benzene ring were observed at 1655 cm−1. Moreover, the structure of PI copolymer was determined by 1H NMR

Conclusions

In this study, a new composite ultrafiltration membrane was prepared with a PI polymer material. The molecular weight of the PI membrane is 10 kDa, and it has a high flux and retention rate. The PI membrane has an excellent antifouling performance and a satisfactory water flux recovery ratio of 90.03%. In addition, the membrane can maintain high performance and stable operation under strong acidic and solvent conditions owing to its good heat resistance and stable structure, thus expanding its

Acknowledgments

This work was financially supported by the National Key R&D Program of China (No. 2017YFC0403903). Assistance from the National Natural Science Foundation of China (No. 21706231) is also acknowledged.

References (41)

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