Temperature-Responsive Nanofibrous Membranes Fabricated by Subsurface-Initiated Atom Transfer Radical Polymerization for Controllable Oil/Water Separation

doi:10.6023/A20090449

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (3): 353-360.DOI: 10.6023/A20090449 Previous Articles Next Articles

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亚表面引发原子转移自由基聚合构筑温度响应型纳米纤维油水分离膜

李乐乐^a^,^b, 向阳阳^a^,^b, 刘欢^a^,^b, 麻拴红^a, 李斌^a, 马正峰^a, 魏强兵^b, 于波^a^,^*(), 周峰^a^,^*()

a 中国科学院兰州化学物理研究所固体润滑国家重点实验室兰州 730000
b 西北师范大学化学化工学院生态功能高分子材料教育部重点实验室甘肃省高分子材料重点实验室兰州 730070

投稿日期:2020-09-27 发布日期:2021-01-05
通讯作者: 于波, 周峰
作者简介:
* E-mail: yubo@licp.cas.cn;
* E-mail: zhouf@licp.cas.cn; Tel.: 0931-4968466
# 李斌, 目前地址: Physik Department, Technische Universität München. James-Franck-Straße 1, D-85748 Garching.
基金资助:
项目受国家自然科学基金(52065061); 项目受国家自然科学基金(51805514); 项目受国家自然科学基金(51705507); 中国科学院国际合作局(121B62KYSB2017009); 中国科学院前沿科学重点研究项目(QYZDY-SSW-JSC013)

Temperature-Responsive Nanofibrous Membranes Fabricated by Subsurface-Initiated Atom Transfer Radical Polymerization for Controllable Oil/Water Separation

Lele Li^a^,^b, Yangyang Xiang^a^,^b, Huan Liu^a^,^b, Shuanhong Ma^a, Bin Li^a, Zhengfeng Ma^a, Qiangbing Wei^b, Bo Yu^a^,^*(), Feng Zhou^a^,^*()

a State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
b Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

Received:2020-09-27 Published:2021-01-05
Contact: Bo Yu, Feng Zhou
Supported by:
National Natural Science Foundation of China(52065061); National Natural Science Foundation of China(51805514); National Natural Science Foundation of China(51705507); Bureau of International Cooperation, Chinese Academy of Sciences(121B62KYSB2017009); Key Research Projects of Frontier Science of Chinese Academy of Sciences(QYZDY-SSW-JSC013)

Subsurface-initiated polymerization is a novel modification strategy for the preparation of covalently embedded polymer brushes. It shows great advantages in the development of polymer brush-functionalized surface with high stability. In this work, the electrospun polyacrylonitrile (PAN) based nanofibrous membrane was modified by subsurface-initiated atom transfer radical polymerization (sSI-ATRP). Covalently embedded poly(N-isopropylacrylamide) (PNIPAM) brushes were grafted from nanofibrous membranes to prepare temperature-responsive oil/water separation membrane (PAN-sg-PNIPAM). When the temperature is lower than the lower critical solution temperature (LCST), strong hydrogen bond interaction between PNIPAM chains and water molecules makes polymer chains fully extended. The membranes are hydrophilic and show very low underwater oil adhesion, resulting in a very high separation efficiency for oil-water emulsions (up to 98.7%). While the temperature is higher than LCST, PNIPAM chains dehydrate and collapse, the membranes become more hydrophobic and the underwater oil adhesion increases significantly. Thus, the separation efficiency dramatically decreases to as low as 9.1%. In addition, due to the high stability and durability of covalently embedded polymer brushes, the membrane can maintain a very stable permeation flux after reversible switch between 20 ℃ and 45 ℃ for 10 cycles under a pressure of 4 kPa. This study provides a novel method for the development of highly stable, durable and smart oi/water separation membranes.

Key words: subsurface initiated polymerization, atom transfer radical polymerization, nanofibrous membranes, temperature-responsive polymer brush, controllable oil/water separation

Cite this article

Lele Li, Yangyang Xiang, Huan Liu, Shuanhong Ma, Bin Li, Zhengfeng Ma, Qiangbing Wei, Bo Yu, Feng Zhou. Temperature-Responsive Nanofibrous Membranes Fabricated by Subsurface-Initiated Atom Transfer Radical Polymerization for Controllable Oil/Water Separation[J]. Acta Chimica Sinica, 2021, 79(3): 353-360.

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Fig. & Tab. 8

Scheme 1. Schematic diagram of preparation and separation process of temperature-responsive oil-water separation membrane

Figure 1. The SEM surface morphology nanofibrous membranes and diameter distribution nanofibers of blank PAN-Br membrane (a) and PAN-sg-PNIPAM membrane (b)

Figure 2. XPS characterization of blank PAN-Br and PAN-sg-PNIPAM nanofibrous membranes. (a) XPS survey spectra; (b) N1s spectra

Figure 3. Water and underwater oil wettability of temperature-responsive membranes. (a) Water contact angles of blank PAN membrane and PAN-sg-PNIPAM membrane at 20 ℃(＜LCST) and 45 ℃(>LCST), respectively; (b) underwater oil contact angles of PAN-sg-PNIPAM membrane at 20 ℃(＜LCST) and 45 ℃(>LCST)

Figure 4. Underwater oil adhesion of temperature-responsive PAN-sg-PNIPAM membrane. (a) Optical snapshots of dynamic adhesion measurements of oil droplet on membranes at 20 ℃(＜LCST) and 45 ℃(>LCST); (b) real-time recorded force-distance curves during the dynamic adhesion measurements; (c) the underwater rolling behavior of different oil droplets on tilted membrane surface at 20 ℃(＜LCST); (d) the underwater rolling behavior of different oil droplets on tilted membrane surface at 45 ℃(>LCST)

Figure 5. Flux and mechanical properties of temperature-responsive PAN-sg-PNIPAM membrane. (a) Flux at 20 ℃(＜LCST) and 45 ℃(>LCST) at the pressure in the range of 2~10 kPa; (b) flux of membrane at 4 kPa switched between 20 ℃ and 45 ℃; (c) the mechanical properties of PAN-Br, PAN-sg-PNIPAM and PAN-sg-PNIPAM membrane after 10 cycles of oil/water separation tests

Scheme 2. The conformational changes of the temperature-responsive PAN-sg-PNIPAM membranes at different temperatures

Figure 6. Controllable separation of emulsion using temperature-responsive PAN-sg-PNIPAM membrane at 20 ℃(＜LCST) and 45 ℃(>LCST). (a~c) Optical microscopic images of emulsion before and after separation; (a1~c1) dynamic light scattering (DLS) analysis of oil droplets size distribution; (d) optical images of dyed emulsion before and after separation; (e) UV spectra of emulsion before and after separation; (f) separation efficiency at 20 ℃ and 45 ℃

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亚表面引发原子转移自由基聚合构筑温度响应型纳米纤维油水分离膜

Temperature-Responsive Nanofibrous Membranes Fabricated by Subsurface-Initiated Atom Transfer Radical Polymerization for Controllable Oil/Water Separation

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