原位合成法制备高通量聚砜超滤膜及其性能研究

doi:10.11949/0438-1157.20200843

摘要/Abstract

摘要：

以聚砜（PSF）为原料，N，N‐二甲基甲酰胺（DMF）为溶剂，4，4'-二氨基二苯砜（DDS）和均苯四甲酸二酐（PMDA）为添加物，在聚砜铸膜液中“原位合成”聚酰胺酸（PAA），采用浸没沉淀相转化法制备高水通量PSF超滤膜。使用傅里叶变换红外光谱仪（ATR-FTIR）和X射线光电子能谱分析（XPS）对膜表面化学组成进行分析，结果表明成功在膜表面引入PAA。膜的荷电性、水接触角、保湿性和水通量等性能测试表明，改性膜具有良好的保湿性和水渗透性。在0.1 MPa的运行压力下，改性膜的纯水通量和牛血清白蛋白（BSA）截留率均高于纯PSF超滤膜，纯水通量从221.39 L/(m²·h)增加至406.57 L/(m²·h)，截留率从75.75%增加到96.14%；在0.01~0.1 MPa的运行压力范围内，改性膜水通量均高于纯PSF超滤膜。。

关键词: 膜, 超滤, 合成, 聚酰胺酸, 保湿

Abstract:

The polysulfone (PSF) ultrafiltration membranes were prepared with PSF raw material, N,N‐dimethylformamide (DMF), 4,4'-diaminodiphenyl sulfone (DDS) and pyromellitic dianhydride (PMDA) through the method of immersion precipitation phase inversion. Among them, DDS and PMDA were doped into the casting solution of PSF to synthesize polyamic acid (PAA) via “in-situ synthesis” method. The fourier transform infrared spectrometer (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used to analyze the chemical composition of the membrane surface, and the results showed that PAA was successfully introduced into the membrane surface. Performance tests of the membrane's chargeability, water contact angle, moisture retention performance and water flux show that the modified membrane has great moisture retention and water permeability. Under 0.1 MPa operating pressure, the pure water flux and bovine serum albumin (BSA) rejection rate of the modified membrane are higher than that of the pure PSF membrane. The pure water flux increased from 221.39 L/(m²·h) to 406.57 L/(m²·h), and the BSA rejection rate increased from 75.75% to 96.14%.With the operating pressure range of 0.01~0.1 MPa, the water flux of the modified membrane is higher than that of pure PSF membrane.

Key words: membrane, ultrafiltration, synthesis, polyamic acid, moisture retention

中图分类号:

王开珍, 王书浩, 李韵浩, 周勇, 高从堦. 原位合成法制备高通量聚砜超滤膜及其性能研究[J]. 化工学报, 2021, 72(3): 1712-1721.

WANG Kaizhen, WANG Shuhao, LI Yunhao, ZHOU Yong, GAO Congjie. Preparation and performance of high-flux polysulfone ultrafiltration membrane by in-situ synthesis[J]. CIESC Journal, 2021, 72(3): 1712-1721.

图/表 13

图1 错流过滤装置示意图[30]1—水泵; 2—调节阀; 3—缓冲罐; 4—测试单元; 5—膜片; 6—调节阀; 7—渗透罐; 8—压力表; 9—原液罐

Fig.1 Schematic diagram of the cross-flow filter[30]

表1 PSF铸膜液组分

Table 1 Composition of PSF casting solution

Membrane code	PSF/% (mass)	DDS/% (mass)	PMDA/%(mass)	DMF/%(mass)
PSF	15.00	0.00	0.0000	85.00
PSF/PAA-1	15.00	0.20	0.1792	84.62
PSF/PAA-2	15.00	0.40	0.3584	84.24
PSF/PAA-3	15.00	0.60	0.5376	83.86

图2 合成PAA的反应方程式

Fig.2 Reaction equation of PAA synthesis

表2 纯PSF和PSF/PAA超滤膜的性能

Table 2 Performances of the pure PSF and PSF/PAA UF membranes

Membrane code	Casting solution viscosity /(mPa·s)	Average surface pore size /nm
PSF	306±2	11.3
PSF/PAA-1	316±1	11.1
PSF/PAA-2	330±2	10.9
PSF/PAA-3	346±1	10.2

图3 原膜和改性膜的红外光谱

Fig.3 ATR-FTIR spectra of original membrane and modified membranes

图4 引入PAA前（a）后(b)PSF膜C 1s的XPS谱图

Fig.4 XPS spectra of PSF membrane C 1s before (a) and after (b) the introduction of PAA

图5 原膜和改性膜的表面[(a)~(d)]和断面[(e)~(h) ]SEM图

Fig.5 SEM images of surface [(a)—(d)] and cross-section [(e)—(h) ] of original membrane and modified membranes

图6 Image J分析后的SEM图 [(a)~(d) ] 和孔径分布特征 (e)

Fig.6 SEM image [(a)~(d) ] and pore size distribution characteristics (e) after Image J analysis

图7 原膜和改性膜的Zeta电位(a)和水接触角(b)

Fig.7 Zeta potential (a) and water contact angle (b) of original membrane and modified membranes

图8 不同PAA添加量的聚砜超滤膜的纯水通量和BSA截留率

Fig.8 Pure water flux and BSA rejection rate of polysulfone ultrafiltration membranes with different PAA additions

图9 不同压力下原膜和改性膜的纯水通量

Fig.9 Pure water flux of original membrane and modified membrane at different pressures

图10 原膜和改性膜的水滴渗透现象图

Fig.10 Diagram of water penetration phenomenon of original membrane and modified membrane

图11 原膜和改性膜在自然状态下沥干不同天数后的纯水通量

Fig.11 Pure water flux of original membrane and modified membrane after draining for different days in natural state

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