凝固浴组成对PVDF-g-PACMO共聚物膜结构与抗污染性能的影响
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摘要
采用亲水、无毒、生物相容性好、对蛋白质吸附有排斥作用的丙烯酰吗啉(ACMO)对聚偏氟乙烯(PVDF)本体进行亲水改性,研究了凝固浴中不同乙醇含量(乙醇:去离子水的质量比分别为0∶100,15∶85,30∶70,45∶55)对PVDFg-PACMO共聚物膜抗污染性能的影响。结果表明,随着凝固浴中乙醇含量的增加,膜断面孔结构向海绵状转变,膜平均孔径和孔隙率增大,纯水通量增加,牛血清蛋白(BSA)截留率降低,膜表面亲水性增加,抗污染性能提高。当凝固浴中乙醇质量分数为45%时,膜表面BSA的吸附量由115.4μg/cm2降至20.6μg/cm2,通量恢复率高达97.6%,总污染指数低至0.148。因此,通过改变凝固浴中乙醇的含量,能使PVDF-g-PACMO膜表面亲水性明显提高,制得了具有良好抗蛋白质污染能力的改性PVDF膜。
Acryloyl morpholine(ACMO)with hydrophilic,non-toxic,good biocompatibility and inhibiting effect of protein adsorption was adopted to modify polyvinylidene fluoride(PVDF).Based on our previous work,coagulation bath composition with different ethanol content(the mass ratio of ethanol and deionized water of 0∶100,15∶85,30∶70,45∶55)was used to study the influence on the antifouling property of PVDFg-PACMO copolymer membrane.The results show that,with increase of the ethanol content in the coagulation bath,the film thickness reduces,section structure tends to transfer to spongy structure,the average pore diameter and porosity of membrane increase,fracture strength scarcely changes,the pure water flux increases,BSA rejection rate reduces,hydrophilicity increases and pollution resistance is improved obviously.Especially when the ethanol content in the coagulation bath is 45%,the BSA adsorption on membrane surface decreases from115.4μg/cm~2 to 20.6μg/cm~2,the flux recovery rate is up to 97.6% and the total pollution index decreases to 0.148.Therefore,the modified PVDF membrane with excellent surface hydrophilicity and antifouling property is prepared by changing the ethanol content in coagulation bath.
Acryloyl morpholine(ACMO)with hydrophilic,non-toxic,good biocompatibility and inhibiting effect of protein adsorption was adopted to modify polyvinylidene fluoride(PVDF).Based on our previous work,coagulation bath composition with different ethanol content(the mass ratio of ethanol and deionized water of 0∶100,15∶85,30∶70,45∶55)was used to study the influence on the antifouling property of PVDFg-PACMO copolymer membrane.The results show that,with increase of the ethanol content in the coagulation bath,the film thickness reduces,section structure tends to transfer to spongy structure,the average pore diameter and porosity of membrane increase,fracture strength scarcely changes,the pure water flux increases,BSA rejection rate reduces,hydrophilicity increases and pollution resistance is improved obviously.Especially when the ethanol content in the coagulation bath is 45%,the BSA adsorption on membrane surface decreases from115.4μg/cm~2 to 20.6μg/cm~2,the flux recovery rate is up to 97.6% and the total pollution index decreases to 0.148.Therefore,the modified PVDF membrane with excellent surface hydrophilicity and antifouling property is prepared by changing the ethanol content in coagulation bath.
引文
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[2]Miyoshi T,Yuasa K,Ishigami T,et al.Effect of membrane polymeric materials on relationship between surface pore size and membrane fouling in membrane bioreactors[J].Appl.Surf.Sci.,2015,330:351-357.
[3]Liu J,Shen X,Zhao Y,et al.Acryloylmorpholine-grafted PVDF membrane with improved protein fouling resistance[J].Ind.Eng.Chem.Res.,2013,52:18392-18400.
[4]Shen X,Liu J,Feng X,et al.Preliminary investigation on hemocompatibility of poly(vinylidene fluoride)membrane grafted with acryloylmorpholine via ATRP[J].J.Biomed.Mater.Res.,A,2015,103:683-692.
[5]Shen X,Liu J,Zhao Y,et al.Preparation and anti-fouling property of acryloylmorpholine-grafted PVDF membrane:the effect of cross-linking agent[J].Int.Polym.Process.,2016,31:207-216.
[6]Gao A,Liu F,Shi H,et al.Controllable transition from fingerlike pores to inter-connected pores of PLLA membranes[J].J.Membr.Sci.,2015,478:96-104.
[7]Xu J,Tang Y,Wang Y,et al.Effect of coagulation bath conditions on the morphology and performance of PSf membrane blended with a capsaicin-mimic copolymer[J].J.Membr.Sci.,2014,455:121-130.
[8]Xing Q,Dong X,Li R,et al.Morphology and performance control of PLLA-based porous membranes by phase separation[J].Polymer,2013,54:5965-5973.
[9]Deng B,Yu M,Yang X,et al.Antifouling microfiltration membranes prepared from acrylic acid or methacrylic acid grafted poly(vinylidene fluoride)powder synthesized via pre-irradiation induced graft polymerization[J].J.Membr.Sci.,2010,350:252-258.
[10]冯霞,郭艳芬,赵义平,等.凝固浴温度对PVDF-g-PNIPAAm温度敏感膜成膜过程与性能的影响[J].高等学校化学学报,2011,32(6):1424-1430.Feng X,Guo Y F,Zhao Y P,et al.Influence of coagulant temperature on the membrane formation process and properties of PVDF-g-PNIPAAm temperature-sensitive membranes[J].Chemical Journal of Chinese Universities,2011,32(6):1424-1430.
[11]王旭东,张凯,王磊,等.凝固浴组成对热诱导相分离法制备PVDF微孔膜形态结构的影响[J].膜科学与技术,2015,35(5):51-57.Wang X D,Zhang K,Wang L,et al.Effects of coagulation bath composition on structure and morphology of PVDF membrane prepared by thermal induced phase separation method[J].Membrane Science and Technology,2015,35(5):51-57.
[12]Qin H,Sun C,He C,et al.High efficient protocol for the modification of polyethersulfone membranes with anticoagulant and antifouling properties via in situ cross-linked copolymerization[J].J.Membr.Sci.,2014,468:172-183.