Preparation and Modification of PVDF-g-PAA Copolymer on PVDF Membrane
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摘要: 为了改善聚偏氟乙烯（PVDF）膜的亲水性，本文通过自由基聚合法，以水/乙醇混合溶液为溶剂，合成了以PVDF为主链，聚丙烯酸（PAA）为侧链的PVDF-g-PAA两亲性共聚物。通过改变丙烯酸（AA）浓度合成了三种不同接枝率的PVDF-g-PAA共聚物，红外(FT-IR）及热重分析(TGA)结果显示接枝率以AA单体浓度10%为最高。以PVDF-g-PAA共聚物为膜材料，采用浸没沉淀法制备膜，通过扫描电子显微镜（SEM）、接触角测试和过滤实验考察膜的形貌及性能。结果表明，随着接枝率的升高，改性膜的平均孔径及孔隙率随之增大，接触角随之降低，表明其亲水性有很大的改善。在保持较好分离效果的基础上，改性膜的水通量及通量恢复率比原膜分别提高了3.78倍和0.76倍，表明其渗透性能及抗污染性能都有很大改善。
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关键词:
- 抗污染性能
Abstract: In this paper, an amphiphilic copolymer (PVDF-g-PAA) having poly(vinylidene fluoride)(PVDF) backbones and poly(acrylic acid)(PAA) side chains was synthesized via radical polymerization method in water/ethanol mixed solution to improve the hydrophilicity of PVDF membrane. Three PVDF-g-PAA copolymer samples of defferent grafting percentage (GP) were prepared by varying the concentration of AA. The results of Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicate the GP at 10% AA concentration was the maximum among them. The copolymer was cast into membrane via immerse precipitation method. Scanning electron microscopy (SEM)、water contact angle measurement and filtration experiment were applied to evaluated the morphology and performance of membranes. It was found that mean pore size and porosity of modified membranes were increased with the increase of GP, but the contact angle of modified membranes decreased, indicating an improved hydrophilicity. Under high separation performance, the water flux and flux recovery ratio of modified membranes were enhanced by 3.78 times and 0.76 times, respectively, which means the permeate ability and fouling resistance of modified membrane have been great improved.-
Keywords:
- Fouling resistance
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[1]Ji J, Liu F, Hashim N A.Poly(vinylidene fluoride) (PVDF) membranes for fluid separation[J].Reactive & Functional Polymers, 2015, 86:134-153
[2] Guo W S, Ngo H H, Li J X.A mini-review on membrane[J].foulingBioresource Technology, 2012, 122:27-34
[3]苗小郁, 李建生, 王连军.聚偏氟乙烯膜的亲水化改性研究进展[J].材料导报, 2006, 20(3):56-59
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[5]李晓, 陆晓峰, 段伟.射线辐照接枝丙烯酸改性超滤膜[J].膜科学与技术, 2007, 27(2):49-52
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[7]Ochoa N A, Masuelli M, Marchese J.Effect of hydrophilicity on fouling of an emulsified oil wastewater with PVDFPMMA membranes[J].Journal of Membrane Science, 2003, 226(1):203-211
[8] Dong C X, He G H, Li H.Antifouling enhancement of poly(vinylidene fluoride) microfiltration membrane by adding Mg(OH)2 nanoparticles [J].Journal of Membrane Science, 2012, 387-388:40-47
[9] Liu F, Hashim N A, Liu Y T.Progress in the production and modification of PVDF membranes[J].Journal of Membrane Science, 2011, 375:1-27
[10] Venault A, Liu Y H, Wu J R.Low-biofouling membranes prepared by liquid-induced phase separation of the PVDF/polystyrene-b-poly(ethylene glycol) methacrylate blend[J].Journal of Membrane Science, 2014, 450:340-350
[11] Venault A, Ballad M R, Liu Y H.Hemocompatibility of PVDF/PS-b-PEGMA membranes prepared by LIPS process[J].Journal of Membrane Science, 2015, 477:101-114
[12] Liu J, Shen X, Zhao Y P.Acryloylmorpholine-Grafted PVDF Membrane with improved Protein Fouling Resistance[J].Industrial & Engineering Chemistry Research, 2013, 52:18392-18400
[13]卞晓锴, 施柳青, 于洋.粉体辐射接枝丙烯酸的聚偏氟乙烯超滤膜的制备[J].膜科学与技术, 2012, 32(2):10-18
[14] Wang L, Pan K, Li L.Surface Hydrophilicity and Structure of Hydrophilic Modified PVDF Membrane by Nonsolvent Induced Phase Separation and Their Effect on Oil/Water Separation Performance[J].Industrial & Engineering Chemistry Research, 2014, 53:6401-6408
[15] Zhang J, Wang Q Y, Wang Z W.Modification of poly(vinylidene fluoride)/polyethersulfone blend membrane with polyvinyl alcohol for improving antifouling ability[J].Journal of Membrane Science, 2014, 466:293-301
[16] Zhou Q, Lei X P, Li J H.Antifouling, adsorption and reversible flux properties of zwitterionic grafted PVDF membrane prepared via physisorbed free radical polymerization[J].Desalination, 2014, 337:6-15
[17] Deng B, Yu M, Yang X X.Antifouling microfiltration membranes prepared from acrylic acid or methacrylic acid grafted poly(vinylidene fluoride) powder synthesized via pre-irradiation induced graft polymerization[J].Journal of Membrane Science, 2010, 350:252-258
[18] Yu J Z, Zhu L P, Zhu B K.Poly(N-isopropylacrylamide) grafted poly(vinylidene fluoride) copolymers for temperature-sensitive membranes[J].Journal of Membrane Science, 2011, 366:176-183
[19] Liu J, Shen X, Zhao Y P.Acryloylmorpholine-Grafted PVDF Membrane with improved Protein Fouling Resistance[J].Industrial & Engineering Chemistry Research, 2013, 52:18392-18400
[20] Yang X X, Deng B, Liu Z Y.Microfiltration membranes prepared from acryl amide grafted poly(vinylidene fluoride) powder and their pH sensitive behaviour[J].Journal of Membrane Science, 2010, 362:298-350
[21] Brawls D M, Mathieson I, Sutherland I.Pretreatment of poly(vinyl fluoride) and poly(vinylidene fluoride) with potassium hydroxide[J].International Journal of Adhesion and Adhesives, 1996, 16(1):87-95
[22] Li M Z, Li J H, Shao X S.Grafting zwitterionic brush on the surface of PVDF membrane using physisorbed free radical grafting technique[J].Journal of Membrane Science, 2012, 405-406(1):141-148
[23] Zhao X Z, Xuan H X, Qin A W.Improved antifouling property of PVDF ultrafiltration membrane with plasma treated PVDF powder[J].RSC Advances, 2015, 5(1):64526-64533
[24] Xu C Q, Huang W, Lu X.Preparation of PVDF porous membranes by using PVDF-g-PVP powder as an additive and their antifouling property[J].Radiation Physics and Chemistry, 2012, 81(1):1763-1769
[1]Ji J, Liu F, Hashim N A.Poly(vinylidene fluoride) (PVDF) membranes for fluid separation[J].Reactive & Functional Polymers, 2015, 86:134-153
[2] Guo W S, Ngo H H, Li J X.A mini-review on membrane[J].foulingBioresource Technology, 2012, 122:27-34
[3]苗小郁, 李建生, 王连军.聚偏氟乙烯膜的亲水化改性研究进展[J].材料导报, 2006, 20(3):56-59
[4] Kang S, Asatekin A, Mayes A M，et al.Protein antifouling mechanisms of PAN UF membranes incorporating PAN-g-PEO additive[J].Journal of Membrane Science, 2007, 296:42-50
[5]李晓, 陆晓峰, 段伟.射线辐照接枝丙烯酸改性超滤膜[J].膜科学与技术, 2007, 27(2):49-52
[6] Liu F, Hashim N A, Liu Y T.Progress in the production and modification of PVDF membranes[J].Journal of Membrane Science, 2011, 375:1-27
[7]Ochoa N A, Masuelli M, Marchese J.Effect of hydrophilicity on fouling of an emulsified oil wastewater with PVDFPMMA membranes[J].Journal of Membrane Science, 2003, 226(1):203-211
[8] Dong C X, He G H, Li H.Antifouling enhancement of poly(vinylidene fluoride) microfiltration membrane by adding Mg(OH)2 nanoparticles [J].Journal of Membrane Science, 2012, 387-388:40-47
[9] Liu F, Hashim N A, Liu Y T.Progress in the production and modification of PVDF membranes[J].Journal of Membrane Science, 2011, 375:1-27
[10] Venault A, Liu Y H, Wu J R.Low-biofouling membranes prepared by liquid-induced phase separation of the PVDF/polystyrene-b-poly(ethylene glycol) methacrylate blend[J].Journal of Membrane Science, 2014, 450:340-350
[11] Venault A, Ballad M R, Liu Y H.Hemocompatibility of PVDF/PS-b-PEGMA membranes prepared by LIPS process[J].Journal of Membrane Science, 2015, 477:101-114
[12] Liu J, Shen X, Zhao Y P.Acryloylmorpholine-Grafted PVDF Membrane with improved Protein Fouling Resistance[J].Industrial & Engineering Chemistry Research, 2013, 52:18392-18400
[13]卞晓锴, 施柳青, 于洋.粉体辐射接枝丙烯酸的聚偏氟乙烯超滤膜的制备[J].膜科学与技术, 2012, 32(2):10-18
[14] Wang L, Pan K, Li L.Surface Hydrophilicity and Structure of Hydrophilic Modified PVDF Membrane by Nonsolvent Induced Phase Separation and Their Effect on Oil/Water Separation Performance[J].Industrial & Engineering Chemistry Research, 2014, 53:6401-6408
[15] Zhang J, Wang Q Y, Wang Z W.Modification of poly(vinylidene fluoride)/polyethersulfone blend membrane with polyvinyl alcohol for improving antifouling ability[J].Journal of Membrane Science, 2014, 466:293-301
[16] Zhou Q, Lei X P, Li J H.Antifouling, adsorption and reversible flux properties of zwitterionic grafted PVDF membrane prepared via physisorbed free radical polymerization[J].Desalination, 2014, 337:6-15
[17] Deng B, Yu M, Yang X X.Antifouling microfiltration membranes prepared from acrylic acid or methacrylic acid grafted poly(vinylidene fluoride) powder synthesized via pre-irradiation induced graft polymerization[J].Journal of Membrane Science, 2010, 350:252-258
[18] Yu J Z, Zhu L P, Zhu B K.Poly(N-isopropylacrylamide) grafted poly(vinylidene fluoride) copolymers for temperature-sensitive membranes[J].Journal of Membrane Science, 2011, 366:176-183
[19] Liu J, Shen X, Zhao Y P.Acryloylmorpholine-Grafted PVDF Membrane with improved Protein Fouling Resistance[J].Industrial & Engineering Chemistry Research, 2013, 52:18392-18400
[20] Yang X X, Deng B, Liu Z Y.Microfiltration membranes prepared from acryl amide grafted poly(vinylidene fluoride) powder and their pH sensitive behaviour[J].Journal of Membrane Science, 2010, 362:298-350
[21] Brawls D M, Mathieson I, Sutherland I.Pretreatment of poly(vinyl fluoride) and poly(vinylidene fluoride) with potassium hydroxide[J].International Journal of Adhesion and Adhesives, 1996, 16(1):87-95
[22] Li M Z, Li J H, Shao X S.Grafting zwitterionic brush on the surface of PVDF membrane using physisorbed free radical grafting technique[J].Journal of Membrane Science, 2012, 405-406(1):141-148
[23] Zhao X Z, Xuan H X, Qin A W.Improved antifouling property of PVDF ultrafiltration membrane with plasma treated PVDF powder[J].RSC Advances, 2015, 5(1):64526-64533
[24] Xu C Q, Huang W, Lu X.Preparation of PVDF porous membranes by using PVDF-g-PVP powder as an additive and their antifouling property[J].Radiation Physics and Chemistry, 2012, 81(1):1763-1769
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