Preparation and Properties of Modified Polybenzimidazole Solvent Resistant Nanofiltration Membranes

doi:10.19894/j.issn.1000-0518.250107

Chinese Journal of Applied Chemistry ›› 2026, Vol. 43 ›› Issue (2): 259-274.DOI: 10.19894/j.issn.1000-0518.250107

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Preparation and Properties of Modified Polybenzimidazole Solvent Resistant Nanofiltration Membranes

Li-Na JIAO, Chen-Yu WANG, Yu-Ting JIANG, Miao-Miao HE, Dong-Ju CHEN()

School of Chemistry and Chemical Engineering，Liaoning Normal University，Dalian 116029，China

Received:2025-03-14 Accepted:2025-06-24 Published:2026-02-01 Online:2026-03-06
Contact: Dong-Ju CHEN
About author:Dongjuchen_1978@lnnu.edu.cn
Supported by:
the National Natural Science Foundation of China(22075121);the Open Project of State Key Laboratory of Fine Chemicals, Dalian University of Technology(KF2205)

Abstract

Abstract:

With the continuous development of our country's industry， more and more organic waste liquid has been produced. Therefore， the separation of solutes from organic solutions and the recovery of solvents have attracted extensive attention. Compared with traditional separation technologies， nanofiltration has been gradually applied to organic solutions due to its advantages of mild operating conditions and low energy consumption， but it is still a major challenge to develop nanofiltration membranes that can exist stably in organic solvents and have good separation performance. In this study， FeCl₃·6H₂O and ZnSO₄·7H₂O solutions were selected as cross-linking agents to cross-link with polybenzimidazole （OPBI） membranes， and high-performance modified OPBI solvent-resistant nanofiltration membranes were prepared. The morphology and structure of the nanofiltration membranes before and after modification as well as the separation performance were investigated. The experimental results showed that the separation performance of all modified membranes was significantly improved compared with the original OPBI membranes. For example， the retention of rose bengal （RB） in isopropanol （IPA） by the crosslinked OPBI membranes all reached more than 99%. Crosslinked membranes also have good application prospects in drugs and food， with excellent retention of tetracycline in IPA and L-α-lecithin in dichloromethane （DCM）. In addition， the crosslinked membranes also have excellent stability in organic solvents and show good stability in strong polar solvents such as N，N-dimethylformamide （DMF） and N，N-dimethylacetamide （DMAc）.

Key words: Polybenzimidazole, Solvent resistant nanofiltration, Crosslinked, Metal ions, Solvent stability

CLC Number:

O631

Li-Na JIAO, Chen-Yu WANG, Yu-Ting JIANG, Miao-Miao HE, Dong-Ju CHEN. Preparation and Properties of Modified Polybenzimidazole Solvent Resistant Nanofiltration Membranes[J]. Chinese Journal of Applied Chemistry, 2026, 43(2): 259-274.

Figures/Tables 20

Table 1 Naming of original and crosslinked membranes

w（polymer）/%	12%	15%	17.5%
Pristine membranes	OPBI-12	OPBI-15	OPBI-17.5
FeCl₃·6H₂O crosslinked membranes	OPBI-Fe³⁺-12	OPBI-Fe³⁺-15	OPBI-Fe³⁺-17.5
ZnSO₄·7H₂O crosslinked membranes	OPBI-Zn²⁺-12	OPBI-Zn²⁺-15	OPBI-Zn²⁺-17.5

Table 2 Properties of solvents

Solvent	Relative molecular mass/（g·mol^-1）	Molar volume/（m³·mol^-1）	Hansen solubility parameters/（MPa^0.5）	η/（mPa·s）	ρ/（g·cm^-3）
n-Heptane	100.2	144.0	15.3	0.400	0.683
n-Hexane	86.2	127.5	14.9	0.326	0.659
DCM	84.9	67.8	20.3	0.430	1.325
EA	88.1	98.0	18.1	0.450	0.902
MIBK	100.1	125.0	16	0.542	0.796
THF	72.1	79.7	19.4	0.550	0.890
IPA	60.1	75.9	23.6	1.830	0.785
NMP	99.1	98.8	23.0	1.650	1.020
Acetone	58.1	75.1	19.9	0.290	0.791
DMF	73.1	77.0	24.9	0.802	0.947
DMAc	87.1	96.2	22.8	0.920	0.940

Fig.1 （A） FT-IR spectra of FeCl3·6H2O crosslinked 15% OPBI membrane in range of 500~4000 cm-1；（B） 700~1650 cm-1 FT-IR spectra of FeCl3·6H2O crosslinked 15% OPBI membrane in range of 700~1650 cm-1

Fig.2 （A） FT-IR spectra of ZnSO4·7H2O crosslinked 15% OPBI membrane in range of 500~4000 cm-1；（B） FT-IR spectra of ZnSO4·7H2O crosslinked 15% OPBI membrane in range of 200~1800 cm-1

Fig.3 XPS spectra of OPBI-12 and OPBI-Fe3+-12

Fig.4 XPS spectra of OPBI-12 and OPBI-Zn2+-12

Fig.5 SEM images of the original OPBI nanofiltration membrane

Fig.6 SEM images of FeCl3·6H2O cross-linked OPBI nanofiltration membrane

Fig.7 SEM images of ZnSO4·7H2O cross-linked OPBI nanofiltration membrane

Fig.8 Effect of different crosslinking times on the separation performance of OPBI-Fe3+-15 （A） and OPBI-Zn2+-15 （B） membrane

Fig.9 The effect of different crosslinking concentrations on the separation performance of OPBI-Fe3+-15 （A） and OPBI-Zn2+-15 （B） membrane

Fig.10 （A） The pure solvent permeation flux of the original OPBI membrane；（B） The pure solvent permeation flux of FeCl3·6H2O crosslinked OPBI membrane；（C） The pure solvent permeation flux of ZnSO4·7H2O crosslinked OPBI membrane；（D） The relationship between the solvent permeation flux of the OPBI-15 membrane and δp·η-1·v-1

Fig.11 （A） Retention rates of RB in IPA by original and cross-linked OPBI membranes；（B） Permeation flux of RB in IPA by original and cross-linked OPBI membranes；（C） Retention rates of BTB in isopropanol by original and cross-linked OPBI membranes；（D） Permeation flux of BTB in isopropanol by original and cross-linked OPBI membranes；（E） Retention rates of MB in IPA by original and cross-linked OPBI membranes；（F） Permeation flux of MB in IPA by original and cross-linked OPBI membranes

Fig.12 （A） Retention rates of tetracycline in IPA by original and cross-linked OPBI membranes；（B） Permeance of tetracycline in IPA by originaland cross-linked OPBI membranes

Fig.13 （A） Retention rates of L-α-lecithin in DCM by original and cross-linked OPBI membranes；（B） Permeance of L-α-lecithin in DCM by originaland cross-linked OPBI membranes

Table 3 Stability of original and cross-linked OPBI nanofiltration membranes in organic solvents

Membrane	n-Heptane	DCM	EA	n-Hexane	IPA	Ethanol	Acetone	MIBK	MeCN
OPBI-12	—	—	—	—	—	—	—	—	—
OPBI-Fe³⁺-12	—	—	—	—	—	—	—	—	—
OPBI-Zn²⁺-12	—	—	—	—	—	—	—	—	—
OPBI-15	—	—	—	—	—	—	—	—	—
OPBI-Fe³⁺-15	—	—	—	—	—	—	—	—	—
OPBI-Zn²⁺-15	—	—	—	—	—	—	—	—	—
OPBI-17.5	—	—	—	—	—	—	—	—	—
OPBI-Fe³⁺-17.5	—	—	—	—	—	—	—	—	—
OPBI-Zn²⁺-17.5	—	—	—	—	—	—	—	—	—

Table 4 Stability of original and cross-linked OPBI nanofiltration membranes in polar organic solvents

Membrane	THF	DMF	DMAc	NMP
OPBI-12	+	+	+	+
OPBI-Fe³⁺-12	—	-4.3%	-3.7%	-23.6%
OPBI-Zn²⁺-12	—	-3.4%	-2.0%	-3.8%
OPBI-15	-4.5%	+	+	+
OPBI-Fe³⁺-15	—	-1.2%	-2.3%	-16.3%
OPBI-Zn²⁺-15	—	—	-1.2%	-3.1%
OPBI-17.5	-2.2%	+	+	+
OPBI-Fe³⁺-17.5	—	—	—	-7.8%
OPBI-Zn²⁺-17.5	—	—	—	-2.6%

Fig.14 Time dependent changes in the separation performance of RB in THF by cross-linked OPBI membrane

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Preparation and Properties of Modified Polybenzimidazole Solvent Resistant Nanofiltration Membranes

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