本文利用聚偏氟乙烯-三氟氯乙烯（PVDF-CTFE）独有的C-Cl键作为反应活性位点，在配制铸膜液的过程中加入多羟基亲水性物质葡甲胺，PVDF-CTFE在溶解的同时与葡甲胺发生接枝反应，从而基于原位取代反应一步法制备了持久亲水的聚偏氟乙烯-三氟氯乙烯膜。在本文中，我们重点对比了一步法本体改性制备的改性PVDF-CTFE膜与表面接枝改性以及表面交联改性的PVDF-CTFE膜，考察了这三种方式改性后PVDF-CTFE膜的亲水性、拉伸强度、孔径变化和抗污染性能等，结果表明，一步法对共聚物膜的亲水化改性效果（水接触角下降66.2°）以及膜抗污染性能提升效果显著高于其余两种方式，并且在保持膜的孔径和拉伸强度不受影响的前提下显著地提升了膜的纯水通量（最高提升了185%）。

In this paper, the unique C-Cl bond of Poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) (PVDF-CTFE) is used as the reactive site, and the polyhydroxyl hydrophilic substance meglumine, PVDF is added in the process of preparing the casting solution. -CTFE undergoes a grafting reaction with meglumine while dissolving, and a durable hydrophilic polyvinylidene fluoride-trifluorochloroethylene membrane is prepared an one-step substitution reaction which is based on in situ. In this paper, we focused on comparing the modified PVDF-CTFE membrane prepared by one-step bulk modification with surface graft modification and surface cross-linking modified PVDF-CTFE membrane. We examined the hydrophilicity, mechanical properties, pore size change, and antifouling performance of PVDF-CTFE that modified by these three methods. The results show that the one-step method has a hydrophilic modification effect on the copolymer membrane (water contact angle decreased by 66.2 °) and a significant improvement in the antifouling performance of the membrane, it is higher than the other two methods, and significantly improves the pure water flux of the membrane (with a maximum increase of 185%) while maintaining the membrane's pore size and mechanical properties.

[1] Souzy R, Ameduri B. Functional fluoropolymers for fuel cell membranes[J]. Prog. Polym. Sci, 2005, 30:644-687.
[2] Abidin A Z, Puspasari T, NUGROHO W A. Polymers for Enhanced Oil Recovery Technology[J]. Procedia. Chem, 2012, 4:11-16.
[3] Rabuni M F, Sulaiman N M N, Aroua M K, et al. Effects of Alkaline Environments at Mild Conditions on the Stability of PVDF Membrane: An Experimental Study[J].  Ind. Eng. Chem. Res, 2013, 52 (45):15874-15882.
[4] Ranjan V, Yu L, Nardelli M B, et al. Phase Equilibria in High Energy Density PVDF-Based Polymers[J]. Phys. Rev. Lett, 2007, 99 (4):47801.
[5] Zheng L B, Wang J, Li J, et al. Preparation, evaluation and modification of PVDF-CTFE hydrophobic membrane for MD desalination application[J]. Desalination,2007, 402:162-172.
[6] Zheng L B, Wu Z J, Wei Y S, et al. Preparation of PVDF-CTFE hydrophobic membranes for MD application: Effect of LiCl-based mixed additive[J]. J. Membr. Sci, 2016, 506:71-85.
[7] Sousa R E, Kundu M, Gören A, et al. Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion[J]. RSC Adv,2015, 5:90428-90436.
[8] Karkhanechi H, Vaselbehagh M, Jeon S, et al. D.M. Wang, H. Matsuyamaa, Preparation and characterization of polyvinylidenedifluoride-co-chlorotrifluoroethylene hollow fiber membranes with high alkaline resistance[J]. Polym, 2018, 145:310-323.
[9] Guo W S, Ngo HH, Li J X. A mini-review on membrane fouling[J]. Bioresour. Technol, 2012, 122:27-34.
[10] Asatekina A, Kang S, Elimelechb M, et al. Anti-fouling ultrafiltration membranes containing polyacrylonitrile-graft-poly(ethylene oxide) comb copolymer additives[J].  J. Membr. Sci, 2007, 298 (2007) 136-146.
[11] Drews A, Membrane fouling in membrane bioreactors—Characterisation, contradictions, cause and cures[J]. J. Membr. Sci, 2010, 363:1-28.
[12] Yang C, Han N, Han C Y, et al. Design of a Janus F-TiO2@PPS porous membrane with asymmetric wettability for switchable oil/water separation[J]. ACS Appl. Mater. Interfaces,2019, 11:2522408-22418.
[13] Han N, Yang C, Zhang Z X, et al. Electrostatic assembly of a titanium dioxide@hydrophilic poly(phenylene sulfide) porous membrane with enhanced wetting selectivity for separation of strongly corrosive oil-water emulsions[J]. ACS Appl. Mater. Interfaces, 2019, 11:35479-35487.
 [14] Zhang M F, Russell T P. Graft Copolymers from Poly(vinylidene fluoride-\r, c\r, o\r,-chlorotrifluoroethylene) via Atom Transfer Radical Polymerization[J].  Macromol, 2006, 39:3531-3539.
[15] Koh J H, Kim Y M, Park J T, et al. Nanofiltration membranes based on poly(vinylidene-fluoride-co-chlorotrifluoroethylene)-graft-poly(styrene sulfonic acid) [J]. Polym. Adv. Technol, 2010, 19:1643-1648.
[16] Liu F, Abed M R M, LI K. Hydrophilic modification of P(VDF-co-CTFE) porous membranes[J]. Chem. Eng. Sci, 2010, 66:27-35.
[17] Kato K, Uchida E, Kang e T, et al. Polymer surface with graft chains[J]. Progress in Polymer Science, 2003, 28(2): 209-259.
[18] 张庆磊，吕晓龙，刘娟娟，聚偏氟乙烯血液透析膜的制备与评价[C]// 天津市生物医学工程学会第三十四届学术年会. 中国会议，2014.
[19] 蒋文斌, 纪利俊, 陈葵, 等. 聚乙烯醇与戊二醛的交联反应动力学[J]. 华东理工大学学报(自然科学版), 2016, 42(5): 625-629.
[20] 庄银凤, 朱仲祺, 王艳焰, 等. 对聚乙烯醇-戊二醛凝胶体系的初步研究[J]. 油田化学, 1996, 13(3): 264-265.
[21] 邱海龙, 吕晓龙, 武春瑞, 等. 一种筋线增强型聚偏氟乙烯中空纤维膜纺丝条件对膜结构与性能的影响研究[J]. 膜科学与技术, 2019, 4:21-28.