十二烷基硫酸钠（SDS）和强碱（NaOH）对聚酰胺复合纳滤膜的协同调控机理

doi:10.16085/j.issn.1000-6613.2024-0602

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 2225-2237.DOI: 10.16085/j.issn.1000-6613.2024-0602

十二烷基硫酸钠（SDS）和强碱（NaOH）对聚酰胺复合纳滤膜的协同调控机理

薛立新¹^,²(), 董永平²^,³(), 陈梦瑶³, 高从堦³

^1.温州大学化学与材料工程学院，浙江温州 325035
^2.温州大学新材料与产业技术研究院，浙江温州 325024
^3.浙江工业大学化工学院膜分离与水科学技术中心，浙江杭州 310014

收稿日期:2024-04-10 修回日期:2024-07-07 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 薛立新
作者简介:董永平（1999—），男，硕士研究生，研究方向为膜科学与技术。E-mail：Q1797754632@outlook.com。
基金资助:
国家自然科学基金(21975222)

Synergistic regulation mechanism of sodium dodecyl sulfate (SDS) and strong base (NaOH) on polyamide composite nanofiltration memrbanes

XUE Lixin¹^,²(), DONG Yongping²^,³(), CHEN Mengyao³, GAO Congjie³

^1.School of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China
^2.Institute of New Materials and Industrial Technology, Wenzhou University, Wenzhou 325024, Zhejiang, China
^3.Center for Membrane Separation & Water Science and Technology, College of Chemical Engineering, Zhejiang University of Techonology, Hangzhou 310014, Zhejiang, China

Received:2024-04-10 Revised:2024-07-07 Online:2025-04-25 Published:2025-05-07
Contact: XUE Lixin

摘要/Abstract

摘要：

针对传统聚酰胺复合（TFC-PA）纳滤（NF）膜溶剂渗透性和溶质分离选择性相互制约、无法同时提升的问题，本文从界面聚合调控出发，由适当比例表面活性剂十二烷基硫酸钠（SDS）和强碱（NaOH）组成二元调节剂。其中，SDS单分子层通过静电作用富集哌嗪（PIP），包裹有机酰氯避免其被NaOH水解，同时降低界面张力，加快PIP分子跨界面均匀扩散，提高界面聚合的速度和均匀性；适量的NaOH吸酸保持SDS的表面活性，同时去质子化活化PIP，加快界面聚合速度，形成均匀聚酰胺分离层。这种协同增强效应使在水相溶液含有0.35%（质量体积浓度）SDS和0.3%（质量体积浓度）NaOH条件下，生成的聚酰胺复合膜MPA-SDS-NaOH与TFC-PA NF膜相比，聚酰胺层交联度从44.8%提高到88.4%，孔径分布变窄的同时，厚度从125nm降到42nm，渗透通量从的6.04L/(m²·h·bar)提高到19.20L/(m²·h·bar)（1bar=0.1MPa），NaCl和Na₂SO₄的单盐分离选择性也从29.4上升到152.6，实现了膜渗透通量和分离选择性的同时提升。SDS和NaOH协同补偿调控策略为制备高渗透选择性脱盐聚酰胺纳滤膜提供了新的思路。

关键词: 协同效应, 界面聚合调控, 选择性, 纳滤膜, 聚酰胺复合膜

Abstract:

To overcome the "trade-off" between the solvent permeability and solute separation selectivity of traditional thin film polyamide composite (TFC-PA) nano filtration (NF) membrane, the interface polymerization (IP) was regulated by dodecyl sulfate (SDS) and strong base (NaOH) in the aqueous phase. Presence of SDS could reduce interface tension, enrich PIP monomer through electrostatic interaction, protect poly(acyl chloride) monomer from hydrolysis and accelerate the uniform diffusion of PIP molecules across interfaces, leading to improved reaction speed and uniformity in the interface polymerization, while NaOH further accelerated the interface polymerization by absorbing the produced acid to keep the activity of SDS as surfactant and also de-protonating PIP monomer for faster reaction. This synergistic enhancement effect enabled the PA layer of generated composite membrane MPA-SDS-NaOH with aqueous phase containing 0.35%SDS and 0.3%NaOH to have narrowed pore size, increased crosslinking degree from 44.8% to 88.4%, decreased thickness from 125nm to 42nm, leading to increased water permeance from 6.04L/(m²·h·bar) to 19.20L/(m²·h·bar), and increased separation selectivity of NaCl and Na₂SO₄ from 29.4 to 152.6. This cooperative compensatory regulation strategy of SDS and NaOH may provide new avenues for preparing highly permeable and selective TFC-PA NF membranes.

Key words: synergistic effect, interface polymerization regulation, selectivity, nanofiltration membrane, polyamide composite membrane

中图分类号:

TQ028

薛立新, 董永平, 陈梦瑶, 高从堦. 十二烷基硫酸钠（SDS）和强碱（NaOH）对聚酰胺复合纳滤膜的协同调控机理[J]. 化工进展, 2025, 44(4): 2225-2237.

XUE Lixin, DONG Yongping, CHEN Mengyao, GAO Congjie. Synergistic regulation mechanism of sodium dodecyl sulfate (SDS) and strong base (NaOH) on polyamide composite nanofiltration memrbanes[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2225-2237.

图/表 15

图1 线性部分结构单元和交联部分结构单元

图2 低压膜性能评价仪和错流过滤示意图

图3 MPA、MPA-SDS0.35%、MPA-NaOH0.3%和MPA-SDS0.35%-NaOH0.3%膜的红外谱图、X射线光电子能谱图、交联度和元素精细谱

图4 荷电性和亲水性变化

图5 界面张力变化

图6 MPA、MPA-SDS0.35%、MPA-NaOH0.3%和MPA-SDS0.35%-NaOH0.3%膜横截面形貌SEM图

图7 MPA、MPA-SDS0.35%、MPA-NaOH0.3%和MPA-SDS0.35%-NaOH0.3%的表面SEM图

图8 MPA、MPA-SDS0.35%、MPA-NaOH0.3%和MPA-SDS0.35%-NaOH0.3%的2D/3D AFM图

图9 PEG的截留率和孔径分布

表1 不同纳滤膜的MWCO、孔径和几何标准偏差

膜类型	µ_p/nm	σ_p/nm	MWCO/Da
MPA	0.267	1.58	431.78
MPA-SDS_0.35%	0.263	1.48	351.13
MPA-NaOH_0.3%	0.274	1.51	397.33
MPA-SDS_0.35%-NaOH_0.3%	0.208	1.46	228.47

图10 MPA膜随SDS和NaOH浓度变化的渗透脱盐性能

图11 MPA-SDS-NaOH膜随SDS、NaOH浓度变化的渗透脱盐性能

图12 不同类型纳滤膜脱盐性能和单盐选择性能比较

图13 操作压力和盐浓度对MPA-SDS0.2%-NaOH0.32%性能影响

图14 MPA-SDS0.2%-NaOH0.32% 24h分离性能、MPA-SDS0.35%-NaOH0.3%与商品膜及文献中膜的性能对比

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十二烷基硫酸钠（SDS）和强碱（NaOH）对聚酰胺复合纳滤膜的协同调控机理

Synergistic regulation mechanism of sodium dodecyl sulfate (SDS) and strong base (NaOH) on polyamide composite nanofiltration memrbanes

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