微乳液聚合耦合共混法构建聚偏氟乙烯共混杂化膜

doi:10.7503/cjcu20190189

摘要/Abstract

摘要：

以苯乙烯和甲基丙烯酸甲酯混合物作为油相, 采用反相微乳液法制备了AgCl纳米粒子; 通过微乳液原位聚合油相单体得到包含AgCl纳米粒子的聚合乳液; 将聚合乳液与聚偏氟乙烯(PVDF)通过共混法构建了包含AgCl纳米粒子的PVDF共混杂化膜. 紫外-可见光谱、透射电子显微镜(TEM)及扫描电子显微镜(SEM)等表征结果和超滤实验结果表明, 聚合乳液加入的同时引入了亲水性聚合物和表面亲水的AgCl纳米粒子, 不仅改善了PVDF共混杂化膜的孔隙率和平均孔径, 还显著增强了PVDF共混杂化膜的极性和亲水性, 最终提升了膜的水通量和抗污染性能; 过量聚合乳液加入后不能与PVDF材料均匀共混, 而且AgCl纳米粒子也会在膜中形成团聚物堵塞膜孔隙, 从而削弱了膜的水通量和抗污染性能.

关键词: 微乳液聚合, 共混, PVDF膜, AgCl纳米粒子, 超滤

Abstract:

AgCl nanoparticles were obtained in the reverse microemulsion using styrene and methyl methacrylate mixture as an oil phase. And then, polymer emulsion containing AgCl nanoparticles was obtained through in-situ polymerization of oil monomers in the microemulsion. Finally, polyvinylidene fluoride(PVDF) blending hybrid membranes containing AgCl nanoparticles were constructed by blending method. The results from the structural characterization and ultrafiltration experiments, such as UV-visible spectroscopy, transmission electron microscopy(TEM), and scanning electron microscopy(SEM), showed that the addition of some polymer emulsion combined with hydrophilic polymer and AgCl nanoparticles with hydrophilic surface did not only improve the porosity and average pore size of the PVDF blending hybrid membranes, but also enhanced the polarity and hydrophilicity of the hybrid membranes, thus increasing the water flux and antifouling performance of the membranes. However, the addition of excess polymer emulsion could not blend uniformly with PVDF. Moreover, AgCl nanoparticles would form agglomerates in the membrane to clog the membrane pores. Thereby, the water flux and antifouling performance of the membranes were both weakened.

Key words: Microemulsion polymerization, Blending, Polyvinylidene fluoride membrane, AgCl nanoparticles, Ultrafiltration

中图分类号:

O631

TrendMD:

刘子豪,肖汉,姚远,王挺,吴礼光,张雪杨. 微乳液聚合耦合共混法构建聚偏氟乙烯共混杂化膜. 高等学校化学学报, 2019, 40(10): 2248.

LIU Zihao,XIAO Han,YAO Yuan,WANG Ting,WU Liguang,ZHANG Xueyang. Fabrication of PVDF Hybrid Blending Membrane via Microemulsion Polymerization Coupling with Blending Method ^†. Chem. J. Chinese Universities, 2019, 40(10): 2248.

图/表 13

Table 1 Preparation conditions for different AgCl/P(MMA-St)/PVDF blend membranes*

Membrane	Addition amount of polymer emulsion containing AgCl nanoparticles/g	Mass fraction of polymer emulsion in PVDF blend membranes(%)	Membrane	Addition amount of polymer emulsion containing AgCl nanoparticles/g	Mass fraction of polymer emulsion in PVDF blend membranes(%)
PVDF	0	0	PVDF-15	0.9	15
PVDF-5	0.3	5	PVDF-30	1.8	30
PVDF-10	0.6	10	PVDF-50	3.0	50

Scheme 1 Preparation of AgCl/P(MMA-St)/PVDF blend membrane

Fig.1 UV-Vis spectra of AgCl-containing reverse microemulsion with different time

Fig.2 TEM image of AgCl nanoparticles generated in the reverse microemulsion

Fig.3 Effect of AgCl nanoparticles on the viscosity of polymer emulsion

Fig.4 TEM image of AgCl nanoparticles in polymer emulsion

Fig.5 FTIR spectra of PVDF and different PVDF composite ultrafiltration membranes

Fig.6 SEM images of surface of different membranes (A)PVDF; (B) PVDF-5; (C)PVDF-10; (D) PVDF-15; (E) PVDF-30; (F) PVDF-50.

Fig.7 SEM images of cross-section of different membranes (A) PVDF; (B) PVDF-5; (C) PVDF-10; (D) PVDF-15; (E) PVDF-30; (F) PVDF-50.

Table 2 Porosity(ε), mean pore size(rm) and Zeta potential of PVDF and PVDF blending ultrafiltration membranes

Membrane	ε(%)	r_m/nm	Zeta potential/mV	Membrane	ε(%)	r_m/nm	Zeta potential/mV
PVDF	30.2±0.1	35.1	-22	PVDF-15	73.6±0.2	69.7	-75
PVDF-5	59.9±0.2	61.2	-51	PVDF-30	59.1±0.3	55.7	-61
PVDF-10	69.8±0.3	59.2	-63	PVDF-50	55.3±0.3	56.5	-58

Fig.8 Water contact angle of PVDF and different PVDF composite ultrafiltration membranes (A) PVDF; (B) PVDF-5; (C) PVDF-10; (D) PVDF-15; (E) PVDF-30; (F) PVDF-50.

Fig.9 Pure water flux(Jw), BSA solution flux(Jp), recovery flux(Jr), and the flux recovery ratio(FRR) of different membranes a. PVDF; b.PVDF-5; c. PVDF-10; d. PVDF-15; e. PVDF-30; f. PVDF-50.

Fig.10 Anti-fouling ratio and the rejection ratio to BSA solution of different membranes a. PVDF; b.PVDF-5; c. PVDF-10; d. PVDF-15; e. PVDF-30; f. PVDF-50.

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