膜科学与技术

热致相分离法聚偏氟乙烯膜的制备及应用

作者：唐元晖¹，林亚凯²，李倩¹，尤功²，马文中¹，王晓琳¹

单位： 1. 清华大学化学工程系膜材料与工程北京市重点实验室，北京 100084；

关键词：热致相分离；聚偏氟乙烯；水处理；膜制备

出版年,卷(期):页码： 2015,35(2):98-107

摘要：

本文以课题组通过热致相分离法（TIPS）制备聚偏氟乙烯（PVDF）超微滤膜及其产业化的相关工作为基础，从PVDF材料性能及其超微滤膜制备方法出发，全面回顾了课题组在TIPS法PVDF膜制备方面的研究历程，包括稀释剂和非溶剂的探索，纳米粒子、共聚物、两性离子等对PVDF膜的改性研究以及PVDF中空纤维膜组件的研制和规模化生产等等，最后还简要介绍了膜组件在不同工业领域的应用情况。

Preparation and application of polyvinylidene fluoride (PVDF) membranes via thermally induced phase separation (TIPS) method were reviewed on the basis of our work. To begin with, PVDF property and the preparation techniques of its microfiltration/ ultrafiltration (MF/UF) membranes were introduced. Then our research results on the preparation of PVDF membranes via TIPS method was comprehensively reviewed, including the selections of diluents and non-solvents, the effects of nanoparticles, hydrophilic polymer and zwitterionic polymer on the PVDF membrane properties, as well as the fabrication and production of the PVDF hollow-fiber membranes. In the end, the applications of the PVDF hollow-fiber membrane modules in some industrial fields were presented.

唐元晖（1986~），女，籍贯甘肃省兰州市，博士后，清华大学博士毕业后即在本单位从事博士后工作，从事相转化法膜制备的研究工作

参考文献：

[1]Loeb S,Sourirajan S. High-flow semipermeable membranes for separation of water from saline solutions[J]. AdvChemSer, 1962, 38(1): 117~132.
[2]Loeb S, Sourirajan S. High flow porous membranes for separating water from saline solutions[P]. US Pat: 3133132. 1964-5-12.
[3]高从堦. 膜技术与饮用水处理[C].上海: 2010年膜法市政水处理技术研讨会论文集:2010.
[4]王从厚, 吴鸣. 国外膜工业发展概况[J]. 膜科学与技术, 2002, 22(1): 65~72.
[5]Lux Research, Inc.Membrane industry takes over new markets as it grows to $2.8 billion[EB/OL]. 2011. 10.
[6]王晓琳, 杨健, 徐南平, 高从堦.我国液体分离膜技术现状及展望[J].南京工业大学学报(自然科学版), 2005, 27(5): 104~110.
[7]时均, 袁权, 高从堦, 等. 膜技术手册[M]. 北京: 化学工业出版社, 2001: 336, 362.
[8]时均, 袁权, 高从堦, 等. 膜技术手册[M]. 北京: 化学工业出版社, 2001: 340-341, 363.
[9]田野,林亚凯,王晓琳, 等.聚偏氟乙烯超/微滤膜的制备技术及其应用现状 [J].新材料产业, 2009, 7(2):13-15.
[10]Mulder M. 膜技术基本原理[M]. 李琳. 译. 北京: 清华大学出版社, 1999:50~53.
[11]Hauptschein M. Process for polymerizing vinylidene fluoride [P]. US Pat: 3193539. 1965-7-6.
[12]张明刚. PVDF膜的亲水改性及抗污染性能研究 [D]. 上海：复旦大学, 2007.
[13]许振良, 翟晓东, 陈桂娥. 高孔隙率聚偏氟乙烯中空纤维膜的研究[J]. 膜科学与技术, 2000， 20(4): 10~13.
[14]吕晓龙. 聚偏氟乙烯中空纤维多孔膜制法及产品 [P]. 中国，CN98103153.6, 1998-7-20.
[15]Seiler D A. PVDF in the chemical process industry: Modern Fluoropolymers[M], Scheirs J ed. Chichester: Wiley 1997:487~505.
[16]李玉芳. 聚偏氟乙烯树脂的生产和应用前景 [J]. 国外塑料, 2010, 28(2):37-41.
[17]Uragami T, Naito Y, Sugihara M. Studies on synthesis and permeability of special polymer membranes [J]. Polymer Bull, 1981, 4(10): 617~622.
[18]Munari S, Bottino A, Capannelli G. Casting and performance of polyvinylidene fluoride based membranes [J]. J MembrSci, 1983, 16(DEC): 181~193.
[19]Shipman G H, Grove C. Microporous sheet material, method of making and articles made therewith [P]. US Pat: 4539256. 1985-9-3.
[20]时均, 袁权, 高从堦, 等. 膜技术手册[M]. 北京: 化学工业出版社, 2001: 43~45.
[21]Liu F, Hashim N A, Liu Y, Abed M R M, Li K. Progress in the production and modification of PVDF membranes[J]. J MembrSci, 2011, 375(1-2):1~27.
[22]Yin X L, Cheng H B, Wang X, Yao Y X. Morphology and properties of hollow-fiber membrane made by PAN mixing with small amount of PVDF[J]. J MembrSci, 1998, 176(2):179~184.
[23]Bottino A, Camera-Roda G, Capannelli G, Munari S. The formation of microporouspolyvinylidenedifluoridemembranes by phase separation[J]. J MembrSci, 1991,57(1): 1~20.
[24]Bottino A, Capannelli G, Munari S, Turturro A. Solubility parameters of poly(vinylidene fluoride)[J]. J PolymSci, Part B: PolymPhys, 1988, 26(4): 785~794.
[25]Li Q, Xu Z L, Yu L Y. Effect of mixed solvents and PVDF types on performances of PVDF microporous membranes[J]. J ApplPolymSci, 2010, 115(4): 2277~2287.
[26]顾明浩, 张军, 王晓琳. 聚偏氟乙烯微孔膜制备方法研究进展[J]. 工业水处理, 2006, 26(2): 5~9.
[27]Castro A J. Methods for making microporous products [P]. US Patent No:4247298, 1981-1-27.
[28]Lloyd D R, Kim S S, Kinzer K E. Microporous membrane formation via thermally induced phase separation. II. Liquid-liquid phase separation[J]. J MembrSci, 1991, 64(3):1~11.
[29]Kim S S, Lloyd D R. Microporous membrane formation via thermally induced phase separation. III. Effect of thermodynamic interactions on the structure of isotactic polypropylene membranes[J]. J MembrSci, 1991, 64(3):13~29.
[30]Doi Y, Matsumura H. Polyvinylidene fluoride porous membrane and a method for producing the same [P]. US Pat: 5022990. 1991-9-3.
[31]Lloyd D R, Kinzer K E, Tseng H S. Microporous membrane formation via thermally induced phase separation. I. Solid-liquid phase separation[J]. J MembrSci, 1990,52(3): 239~261.
[32]Tang Y H, Lin Y K, Ma W Z, Tian Y, Yang J, Wang X L. Preparation of microporous PVDF membrane via TIPS method using binary diluent of DPK and PG[J]. J ApplPolymSci,2010, 118(6):3518~3523.
[33]Su Y, Chen C X, Li J G, Li J D, PVDF membrane formation via thermally induced phase separation[J]. J MacromolSci Part A-Pure ApplChem, 2007, 44(1): 99~104.
[34]Yang J, Wang X L, Tian Y, Lin Y K, Tian F. Morphologies and crystalline Forms of Polyvinylidene Fluoride Membranes Prepared in Different Diluents by Thermally Induced Phase Separation[J]. J PolymSci Pt B-PolymPhys, 2010,48(23): 2468~2475.
[35]CuiA H, Zhen L, Xiao C F, Zhang Y F, Effect of micro-sized SiO2-particle on the performance of PVDF blend membranes via TIPS[J]. J MembrSci, 2010, 360(1~2): 259~264.
[36]Pan B J, Zhu L, Li X F. Preparation of PVDF/CaCO3 composite hollow fiber membrane via a thermally induced phase separation method[J].Polym Compos, 2013, 34 (7): 1204~1210.
[37]Shi F M, Ma Y X, Ma J, Wang P P, Sun W X. Preparation and characterization of PVDF/TiO2 hybrid membranes with ionic liquid modified nano-TiO2 particles[J]. J MembrSci, 2013, 427: 259~269.
[38]Lu X L, Li X F. Preparation of polyvinylidene fluoride membrane via a thermally induced phase separation using a mixed diluent. J ApplPolymSci, 2009, 114 (2): 1213~1219.
[39]Liu M, Xu Z L, Chen D G, Wei Y M. Preparation and characterization of microporous PVDF membrane by thermally induced phase separation from a ternary polymer/solvent/non-solvent system.Desalin Water Treat, 2010, 17 (1~3): 183~192.
[40]Song Z Y, Xing M H, Zhang J, Li B A, Wang S C. Determination of phase diagram of a ternary PVDF/gamma-BL/DOP system in TIPS process and its application in preparing hollow fiber membranes for membrane distillation[J]. Sep PurifTechnol, 2012, 90: 221~230.
[41]Yen C, He H Y, Lee L J, Ho W S W. Synthesis and characterization of nanoporouspolycaprolactone membranes via thermally- and nonsolvent induced phase separations for biomedical device application[J]. J MembrSci,2009(1~2), 343:180~188.
[42]Cui ZY, Xu YY, Zhu LP, Wang JY, Xi ZY, Zhu BK. Preparation of PVDF/PEO-PPO-PEO blend microporous membranes for lithium ion batteries via thermally induced phase separation process. J MembrSci,2008, 325(2):957~963.
[43]杨健.热致相分离制备聚偏氟乙烯微孔结构热力学研究[D]. 北京: 清华大学化学工程系, 2006.
[44]Yang J, Li D W, Lin Y K, Wang X L, Tian F, Wang Z, Formation of a bicontinuous structure membrane of polyvinylidene fluoride in diphenyl ketone diluent via thermally induced phase separation[J]. J ApplPolymSci, 2008, 110 (1): 341~347.
[45]Lin Y K, Tang Y H, Ma H Y, Yang J, Tian Y, Ma Z W, Wang X L, Formation of a bicontinuous structure membrane of polyvinylidene fluoride in diphenyl carbonate diluent via thermally induced phase separation[J]. J ApplPolymSci,2009, 114 (3): 1523~1528.
[46]Tang Y H, Lin Y K, Ma W Z, TianY, Yang J, Wang X L, Preparation of microporous PVDF membrane via tips method using binary diluent of DPK and PG[J].J ApplPolymSci, 2010, 118(6):3518~3523.
[47]Ma W Z, Zhang J, Van der Bruggen B, Wang X L,Formation of an interconnected lamellar structure in PVDF membranes with nanoparticles addition via solid-Liquid thermally Induced phase separation[J]. J ApplPolymSci, 2013, 127(4):3715~3723.
[48]Ma W Z, Zhou B, Liu T Y, Zhang J, Wang X L, The supramolecular organization of PVDF lamellae formed in diphenyl ketone dilutions via thermally induced phase separation[J]. Colloid PolymSci, 2013, 291(4): 981~992.
[49]Ma W Z, Chen S J, Zhang J, Wang X L. Kinetics ofthermally induced phase separation in the PVDF blend/methyl salicylate system and its effect on membrane structures[J], J MacromolSci Part B-Phys, 2011, 50 (1): 1~15..
[50]Li Q, Bi Q Y, Lin H H,Bian L X, Wang X L. A novel ultrafiltration (UF) membrane with controllable selectivity for protein separation[J]. J MembrSci, 2013, 427: 155~167.
[51]Bi Q Y, LI Q, Tian Y, Lin Y K, Wang X L. The hydrophilic modification of PVDF membrane with PVP via a cross-linking reaction[J]. J ApplPolymSci, 2012, 127(1): 394~401.
[52]Li Q, Bi Q Y,Zhou B, Wang X L. Resistance to Protein and Oil Fouling of Sulfobetaine-Grafted Poly(vinylidene Fluoride) Hollow Fiber Membrane and the Electrolyte-Responsive Behavior inNaCl Solution[J]. Appl Surf Sci, 2012, 258(19): 7480~7489.
[53]Li Q, Zhou B,Bi Q Y,Wang X L. Surface modification of PVDF membranes with sulfobetaine polymers for a stably anti-protein-fouling performance[J]. JApplPolym Sci. 2012, 125(5): 4015~4027.
[54]Li Q, Bi Q Y,Zhou B, Wang X L.Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane surface with stably anti-protein-fouling performance via a two-step surface polymerization[J]. Appl Surf Sci, 2012, (258): 4707~4717.

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