低温水等离子体活化和表面接枝DMAE聚氯乙烯中空纤维膜研究

doi:10.11949/0438-1157.20200510

摘要/Abstract

摘要：

采用低温水等离子体技术，在三通道聚氯乙烯(PVC)膜表面接枝了甲基丙烯氧基苄基二甲基氯化铵(DMAE)单体，增强了膜亲水和抗菌性能。通过红外分析，表明DMAE成功接枝到了PVC膜上，水通量提高两倍，PVC-ir-H₂O膜(通过水等离子体处理的膜)对牛血清蛋白(BSA)的吸附能力下降67%，对BSA溶液的通量从7.7提高至40 kg?m^-2?h^-1，并且对BSA的截留能力不变。通过静态及动态抗菌实验，接枝后的PVC膜（PVC-g-PMAE膜）抗菌率达到100%，膜组件运行中的抗菌率也达到82%以上。在保证细菌截留率100%的同时，其渗透通量提高三倍。该膜表面修饰工程技术能实现膜表面的均一化改性，且绿色环保、操作简便、成本低，改性膜在饮用水处理领域，尤其是家用净水器中展现了很好的应用前景。

关键词: 抗菌改性, PVC中空纤维膜, 膜组件, 低温水等离子体, 表面接枝工程

Abstract:

Using low temperature water plasma technology, methacryloxybenzyl dimethyl ammonium chloride (DMAE) monomer was grafted on the surface of the three-channel polyvinyl chloride (PVC) hollow fiber membrane (HFMs) to enhance the membrane??s hydrophilic and antibacterial properties. The ATR-FTIR and contact angle analyses revealed that the antibacterial monomers DMAE were grafted onto the HFMs. The hydrophilicity of membranes was greatly improved, resulting in an enhanced permeation of the H₂O plasma-treated membrane was twice as high as that of the original membrane. At the same time, PVC-ir-H₂O membrane (treated by water plasma technology)exhibited excellent anti-protein absorption ability, of which adsorbing capacity for bovine serum albumin (BSA) decreased by 67% and BSA solution flux increased from 7.7 to 40 kg?m^-2?h^-1. And the BSA rejection of plasma-treated membrane remained at the same level as that of the original membrane, suggesting the membrane surface damage from plasma irradiation could be neglected. Furthermore, the surface modification on HFMs is relatively uniform along the axial direction of fibers and more environment-friendly. In static antibacterial experiments, the grafted HFMs (PVC-g-DMAE) exhibited bactericidal rate of 100% against gram-negative Escherichia coli (E. coli). In dynamic filtration, the grafted module, PVC-g-DMAE, obtained above 82% bactericidal rate in feed tank. Its E. coli solution flux with 100% rejection was increased by three times as much as that of the original one. This activation-grafting technology exhibited well prospect in application of drinking water treatment membrane module, especially small household water purifiers, arising from the facile operation, low cost, and simple.

Key words: antibacterial activity, PVC hollow fiber membrane, membrane module, low-temperature H₂O plasma, graft polymerization

中图分类号:

TQ 028.8

王明兴, 赵欣, 王涛, 路姣姣, 赵之平. 低温水等离子体活化和表面接枝DMAE聚氯乙烯中空纤维膜研究[J]. 化工学报, 2020, 71(9): 4200-4210.

Mingxing WANG, Xin ZHAO, Tao WANG, Jiaojiao LU, Zhiping ZHAO. Study of PVC hollow fiber membrane grafted with DMAE by low-temperature H₂O plasma surface modification[J]. CIESC Journal, 2020, 71(9): 4200-4210.

图/表 17

图1 等离子体装置示意图1—hollow fiber membrane module; 2—discharge coil; 3—pressure sensor; 4—radiofrequency matcher; 5—radiofrequency power source; 6—capacitance gauge; 7—vacuum pump

Fig.1 Scheme of plasma setup

图2 膜动态过滤抗菌实验装置示意图

Fig.2 The membrane filtration setup of dynamic filtration antibacterial experiment

图3 等离子体功率对PVC中空纤维膜接触角的影响等离子体条件：压力（30±3） Pa，辐射时间120 s

Fig.3 The effect of H2O plasma power on water contact angle of PVC hollow fiber membrane

图4 水等离子辐照时间对中空纤维膜接触角的影响等离子体条件：压力（30±3） Pa，功率40 W

Fig.4 The effects of H2O plasma irradiation time on water contact angle of PVC hollow fiber membrane

图5 三通道PVC中空纤维膜的扫描电镜图

Fig.5 SEM images of PVC hollow fiber membrane

图6 不同组件内膜的接触角随距组件入口距离的变化

Fig.6 Dependence of the contact angle of outer surface of membrane on the distance from module inlet for different membrane modules

图7 膜的红外谱图

Fig.7 ATR-FTIR spectra of membranes

图8 PVC膜和PVC-ir-H2O膜的应力变化曲线

Fig.8 Stress-strain curves of original PVC membrane and PVC-ir-H2O

图9 PVC膜、PVC-ir-H2O膜和PVC-g-DMAE膜的孔径分布图

Fig.9 Pore size distributions of the original PVC membrane, PVC-ir-H2O and PVC-g-DMAE

图10 PVC膜、PVC-ir-H2O膜和PVC-g-DMAE膜的纯水通量

Fig.10 Pure water fluxes of PVC membrane, PVC-ir-H2O membrane and PVC-g-DMAE membrane

图11 BSA溶液浓度变化对PVC膜和PVC-ir-H2O膜蛋白吸附量的影响

Fig.11 Anti-adhesion efficacy of PVC and PVC-ir-H2O in contact with different concentration of BSA solution

图12 PVC和PVC-ir-H2O膜组件对BSA溶液的截留率随时间的变化experimental conditions:(20±2)℃, 0.1 MPa

Fig.12 The rejections of original PVC membrane and PVC-ir-H2O modules for BSA solution

图13 PVC膜和PVC-ir-H2O膜的BSA通量随时间的变化JB1—the first time, JB2—the second time, JB3—the third time

Fig.13 BSA solution fluxes of original PVC membrane and PVC-ir-H2O modules

图14 PVC-g-DMAE膜的抗菌性和稳定性

Fig.14 Antibacterial activities and stability of PVC-g-DMAE

图15 PVC膜和PVC-g-DMAE膜对大肠杆菌E. coli的抗菌抑菌照片

Fig.15 Antibacterial inhibition of original PVC membrane and PVC-g-DMAE against E. coli

图16 PVC膜和PVC-g-DMAE膜的动态过滤抗菌活性实验结果

Fig.16 Dynamic filtration antibacterial activities of PVC-g-DMAE

图17 PVC膜和PVC-g-DMAE膜的动态过滤通量随实验次数变化

Fig.17 Dynamic filtration permeation properties of the PVC-g-DMAE

参考文献 39

1	Peters T. Membrane technology for water treatment[J]. Chem. Eng. Technol., 2010, 33: 1233-1240.
2	Tooma M A, Najim T S, Alsalhy Q F, et al. Modification of polyvinyl chloride (PVC) membrane for vacuum membrane distillation (VMD) application[J]. Desalination, 2015, 373: 58-70.
3	Yu Z J, Zhao Y Y, Gao B, et al. Performance of novel Ag-n-TiO₂/PVC reinforced hollow fiber membrane applied in water purification: in-situ antibacterial property and resistance to biofouling[J]. RSC. Adv., 2015, 5: 97320-97329.
4	Mansouri J, Harrisson S, Chen V. Strategies for controlling biofouling in membrane filtration systems: challenges and opportunities[J]. J. Mater. Chem., 2010, 20: 4567-4586.
5	Wang B L, Wang J L, Li D D, et al. Chitosan/poly (vinyl pyrollidone) coatings improve the antibacterial properties of poly(ethylene terephthalate) [J]. Appl. Surf. Sci., 2012, 258: 7801-7808.
6	Waheed S, Ahmad A, Khan S M, et al. Synthesis, characterization, permeation and antibacterial properties of cellulose acetate/polyethylene glycol membranes modified with chitosan[J]. Desalination, 2014, 351: 59-69.
7	Zhu L X, Dai J Y, Chen L, et al. Design and fabrication of imidazolium ion-immobilized electrospun polyurethane membranes with antibacterial activity[J]. J. Mater. Sci., 2017, 52: 2473-2483.
8	Kaner P, Johnson D J, Seker E, et al. Layer-by-layer surface modification of polyethersulfone membranes using polyelectrolytes and AgCl/TiO₂ xerogels[J]. J. Membr. Sci., 2015, 493: 807-819.
9	Luo C, Liu W J, Luo B H, et al. Antibacterial activity and cytocompatibility of chitooligosaccharide-modified polyurethane membrane via polydopamine adhesive layer[J]. Carbohyd. Polym., 2017, 156: 235-243.
10	Xu H, Shi X, Ma H, et al. The preparation and antibacterial effects of dopa-cotton/AgNPs[J]. Appl. Surf. Sci., 2011, 257: 6799-6803.
11	Dolina J, Dlask O, Lederer T, et al. Mitigation of membrane biofouling through surface modification with different forms of nanosilver[J]. Chem. Eng. J., 2015, 275: 125-133.
12	Park S H, Kim S H, Park S J, et al. Direct incorporation of silver nanoparticles onto thin-film composite membranes via arc plasma deposition for enhanced antibacterial and permeation performance[J]. J. Membr. Sci., 2016, 513: 226-235.
13	Mural P K S, Kumar B, Madras G, et al. Chitosan immobilized porous polyolefin as sustainable and efficient antibacterial membranes[J]. ACS Sustain. Chem. Eng., 2016, 4: 862-870.
14	Mauter M S, Wang Y, Okemgbo K C, et al. Antifouling ultrafiltration membranes via post-fabrication grafting of biocidal nanomaterials[J]. ACS Appl. Mater. Inter., 2011, 3: 2861-2868.
15	Xu B S, Niu M, Wei L Q, et al. The structural analysis of biomacromolecule wool fiber with Ag-loading SiO₂, nano-antibacterial agent by UV radiation[J]. J. Photoch. Photobio. A, 2007, 188: 98-105.
16	Lu Z S, Meng M, Jiang Y K, et al. UV-assisted in situ synthesis of silver nanoparticles on silk fibers for antibacterial applications[J]. Colloid Surf. A, 2014, 447: 1-7.
17	Zhao Z P, Li N, Li M S, et al. Controllable modification of polymer membranes by long-distance and dynamic low-temperature plasma flow: long-distance and dynamic characteristics[J]. Plasma Chem. Plasma P, 2012, 32: 1243-1258.
18	Zhao Z P, Li M S, Li N, et al. Controllable modification of polymer membranes by long-distance and dynamic low-temperature plasma flow: a grafting penetrated through electrospun PP fibrous membranes[J]. J. Membr. Sci., 2013, 440: 9-19.
19	Li M S, Zhao Z P, Wang M X, et al. Controllable modification of polymer membranes by LDDLT plasma flow: antibacterial layer onto PE hollow fiber membrane module[J]. Chem. Eng. J., 2015, 265: 16-26.
20	Yao C, Li X S, Neoh K G, et al. Antibacterial activities of surface modified electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) fibrous membranes[J]. Appl. Surf. Sci., 2009, 255: 3854-3858.
21	Mei Y, Yao C, Fan K, et al. Surface modification of polyacrylonitrile nanofibrous membranes with superior antibacterial and easy-cleaning properties through hydrophilic flexible spacers[J]. J. Membr. Sci., 2012, 417/418: 20-27.
22	Gao X L, Wang H Z, Wang J, et al. Surface-modified PSf UF membrane by UV-assisted graft polymerization of capsaicin derivative moiety for fouling and bacterial resistance[J]. J. Membr. Sci., 2013, 445: 146-155.
23	Zhao J, Song L J, Shi Q, et al. Antibacterial and hemocompatibility switchable polypropylene nonwoven fabric membrane surface[J]. ACS Appl. Mater. Inter., 2013, 5: 5260-5268.
24	Asri L A T W, Crismaru M, Roest S, et al. A shape-adaptive, antibacterial-coating of immobilized quaternary-ammonium compounds tethered on hyperbranched polyurea and its mechanism of action[J]. Adv. Funct. Mater., 2014, 24: 346-355.
25	Poverenov E, Shemesh M, Gulino A, et al. Durable contact active antimicrobial materials formed by a one-step covalent modification of polyvinyl alcohol, cellulose and glass surfaces[J]. Colloid. Surface. B., 2013, 112: 356-361.
26	Lu G Q, Wu D C, Fu R W. Studies on the synthesis and antibacterial activities of polymeric quaternary ammonium salts from dimethylaminoethyl methacrylate[J]. React. Funct. Polym., 2007, 67: 355-366.
27	Li M S, Zhao Z P, Li N, et al. Controllable modification of polymer membranes by long-distance and dynamic low-temperature plasma flow: treatment of PE hollow fiber membranes in a module scale[J]. J. Membr. Sci., 2013, 427: 431-442.
28	Zhu D, Cheng H H, Li J N, et al. Enhanced water-solubility and antibacterial activity of novel chitosan derivatives modified with quaternary phosphonium salt[J]. Mat. Sci. Eng. C-Mater., 2016, 61: 79-84.
29	Yanagisawa Y, Yoshioka Y. Remote surface modification of plastics by atmospheric barrier discharge[J]. Electr. Eng. Jpn., 2009, 167: 1-8.
30	Inagaki N, Tasaka S, Horiuchi T, et al. Surface modification of poly(aryl ether ether ketone) film by remote oxygen plasma[J]. J. Appl. Polym. Sci., 1998, 68: 271-279.
31	Yu H Y, Xie Y J, Hu M X, et al. Surface modification of polypropylene microporous membranes to improve their antifouling property in MBR: CO₂ plasma treatment[J]. J. Membr. Sci., 2005, 254: 219-227.
32	Sui Y, Gao X L, Wang Z N, et al. Antifouling and antibacterial improvement of surface-functionalized poly(vinylidene fluoride) membrane prepared via dihydroxyphenylalanine-initiated atom transfer radical graft polymerizations[J]. J. Membr. Sci., 2012, 394/395: 107-119.
33	Chen X, Zhang G F, Zhang Q H, et al. Preparation and performance of amphiphilic polyurethane copolymers with capsaicin-mimic and PEG moieties for protein resistance and antibacteria[J]. Ind. Eng. Chem. Res., 2015, 54: 3813-3820.
34	Kaur S, Ma Z, Gopal R, et al. Plasma-induced graft copolymerization of poly(methacrylic acid) on electrospun poly(vinylidene fluoride) nanofiber membrane[J]. Langmuir, 2007, 23: 13085-13092.
35	Bayramoğlu G, Yalçin E, Arica M Y. Adsorption of serum albumin and γ-globulin from single and binary mixture and characterization of pHEMA-based affinity membrane surface by contact angle measurements[J]. Biochem. Eng. J., 2005, 26: 12-21.
36	Darvishmanesh S, Degrève J, Bruggen B V D. Mechanisms of solute rejection in solvent resistant nanofiltration: the effect of solvent on solute rejection[J]. Phys. Chem. Chem. Phys., 2010, 12: 13333-13342.
37	Yang Y F, Wan L S, Xu Z K. Surface hydrophilization of microporous polypropylene membrane by the interfacial crosslinking of polyethylenimine[J]. J. Membr. Sci., 2009, 337: 70-80.
38	Zhang Y T, Chen Y F, Zhang H Q, et al. Potent antibacterial activity of a novel silver nanoparticle-halloysite nanotube nanocomposite powder[J]. J. Inorg. Biochem., 2013, 118: 59-64.
39	Zodrow K, Brunet L, Mahendra S, et al. Polysulfone ultrafiltration membranes impregnated with silver nanoparticles show improved biofouling resistance and virus removal[J]. Water Res., 2009, 43: 715-723.

[1]	吴降麟, 张朝晖, 王亮, 赵斌, 李腾飞, 陈萌萌. 宽流道反渗透膜元件抗污染性能分析[J]. 化工学报, 2019, 70(4): 1446-1454.
[2]	赵媛媛, 何奎, 李斯陶, 张立志. 中空纤维膜除湿组件的热质传递特性[J]. 化工学报, 2017, 68(S1): 96-104.
[3]	熊长川, 李卫星, 刘业飞, 邢卫红. 柱式膜组件结构的CFD优化设计[J]. 化工学报, 2017, 68(11): 4341-4350.
[4]	张春尧, 耿洪鑫, 郎庆成, 李凭力, 武晓燕. 新型气隙式膜蒸馏组件脱盐过程[J]. 化工学报, 2015, 66(10): 4000-4006.
[5]	李卜义, 王建友, 王济虎, 刘红斌. 新型中空纤维空气隙式膜蒸馏用于海水淡化[J]. 化工学报, 2015, 66(1): 149-156.
[6]	钟文锋1，杨敏林2，左远志2，黄斯珉2. 膜式液体除湿器研究进展[J]. 化工进展, 2013, 32(05): 971-977.
[7]	吕斯濠1，秦琦2，张杰琳3，范洪波1，梁志辉1. 旋转剪切强化膜过滤技术研究进展[J]. 化工进展, 2012, 31(11): 2373-2383.
[8]	华伟1，李传润2，3，张旭2，王虎传3，杨伟华2，徐铜文2，魏凤玉1. 卷式扩散渗析膜法回收H₂SO₄/FeSO₄体系中的H₂SO₄[J]. 化工进展, 2012, 31(01 ): 222-226.
[9]	吕斯濠，张赵田，蔡勋江，范洪波. 振动剪切强化膜过滤技术研究进展 [J]. CIESC Journal, 2009, 28(7): 1115-.
[10]	李昕，王洪海. 改善膜表面流动状态防治膜污染技术的研究进展 [J]. CIESC Journal, 2007, 26(6): 797-.