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

doi:10.6023/A20090449

化学学报 ›› 2021, Vol. 79 ›› Issue (3): 353-360.DOI: 10.6023/A20090449 上一篇下一篇

研究论文

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)

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摘要/Abstract

亚表面引发聚合是一种用于制备共价嵌入型聚合物刷的新型改性策略. 该方法在发展高稳定性聚合物刷功能化表界面材料方面具有显著的优势. 本工作利用亚表面引发原子转移自由基聚合(sSI-ATRP)对静电纺丝聚丙烯腈(PAN)基纳米纤维膜进行亚表面改性, 通过接枝聚N-异丙基丙烯酰胺(PNIPAM)制备了温度响应型纳米纤维油水分离膜(PAN-sg-PNIPAM). 当温度低于低临界溶解温度(LCST)时, PNIPAM链与水分子之间的强氢键作用使得聚合物链完全伸展, 分离膜表面亲水且对油滴具有非常低的粘附力, 对油水乳液具有非常高的分离效率(达98.7%); 当温度高于LCST时, PNIPAM链失水收缩, 膜表面变得更加疏水且对油滴的粘附力显著增加, 其油水乳液分离效率显著降低, 仅为9.1%. 此外, 由于共价嵌入聚合物刷的高稳定性, 该分离膜在4 kPa压力下, 20 ℃和45 ℃之间可逆切换10个循环后, 仍能保持非常稳定的渗透通量. 本研究为发展高稳定性的智能型油水分离膜提供了一种新方法.

关键词: 亚表面引发聚合, 原子转移自由基聚合, 纳米纤维膜, 温度响应聚合物刷, 可控油水分离

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

引用此文

李乐乐, 向阳阳, 刘欢, 麻拴红, 李斌, 马正峰, 魏强兵, 于波, 周峰. 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[J]. 化学学报, 2021, 79(3): 353-360.

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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图/表 8

图式1. 温度响应型油水分离膜的制备及分离示意图

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

图1. 空白PAN-Br膜(a)和PAN-sg-PNIPAM膜(b)的SEM表面形貌及纳米纤维膜的直径分布

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

图2. 空白PAN-Br和PAN-sg-PNIPAM纳米纤维膜的XPS表征. (a) XPS能谱图; (b) N1s能谱

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

图3. 温度响应型膜的水和水下油的润湿性. (a)空白PAN膜和PAN-sg-PNIPAM膜在20 ℃(＜LCST)和45 ℃(>LCST)的水的接触角; (b) PAN-sg-PNIPAM膜在20 ℃(＜LCST)和45 ℃(>LCST)时水下油的接触角

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)

图4. 温度响应PAN-sg-PNIAPM膜的水下油粘附性能. (a) 20 ℃(＜LCST)和45 ℃(>LCST)时油滴在膜上动态粘附测量的光学图片; (b)动态粘附测量过程中实时的力-距离曲线; (c) 20 ℃(＜LCST)时不同油滴在水下倾斜膜表面的滚动行为; (d) 45 ℃(>LCST)时不同油滴在水下倾斜膜表面的滚动行为

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)

图5. 温度响应PAN-sg-PNIPAM膜的通量和力学性能. (a)压力在2~10 kPa范围内在20 ℃(＜LCST)和45 ℃(>LCST)的通量; (b)膜通量在4 kPa时20~45 ℃之间的切换; (c) PAN-Br, PAN-sg-PNIPAM和PAN-sg-PNIPAM膜经10次油水分离后的力学性能

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

图式2. 温度响应型PAN-sg-PNIPAM纤维膜在不同温度下的构象变化

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

图6. 使用温度响应PAN-sg-PNIPAM膜在20 ℃(＜LCST)和45 ℃(>LCST)时乳液的可控油水分离. (a~c)乳液分离前后的光学显微图像; (a1~c1)油滴粒径分布的动态光散射(DLS)分析图; (d)染色乳液分离前后的光学显微图像; (e)乳液分离前后的紫外吸收光谱; (f)在20 ℃和45 ℃的分离效率

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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