1. School of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000, China;
2. Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, China
以Tröger base （TB）和磺化度为20%的磺化聚砜（SPSF）为共混材料，N-甲基-2-吡咯烷酮（NMP）为溶剂，乙二醇单甲醚（EGM）为致孔剂，去离子水为凝固浴，采用非溶剂致相分离法（NIPS）制备了一种新型的SPSF/TB共混超滤膜，考察了共混比对膜结构、水接触角、孔隙率、水通量、BSA截留率和抗污染性能的影响.结果表明，共混之后原有的中性胺及磺酸反应生成了相应的铵盐及磺酸根，表面接触角得以降低，亲水性增强，水通量增加，显著改善了膜的抗污染能力；此外，SPSF/TB膜结构上变成了梯度海绵孔结构，特别是较大共混比时因有机高分子盐的形成，聚合物交联呈现了独特的网状结构.与纯TB膜相比，SPSF/TB3~15膜水通量JWC达到274.92~343.21L/（m2·h）（操作压力为0.1MPa），通量恢复率值（FRR）达到61.11%~67.45%，分别提升了42.88%~78.37%和67.4%~84.8%.在最优条件下，SPSF/TB5对废水中的乳化油截留率可达到98.52%以上，循环3次后水通量和FRR分别趋于199.1L/（m2·h）和61.6%.
Tröger's base (TB) and sulfonated polysulfone (SPSF) with sulfonation degree of 20% as blending materialswere used to prepare a novelSPSF/TB blending ultrafiltration membranes by non-solvent induced phase separation process (NIPS), N-methyl-2-pyrrolidone (NMP), ethylene glycol monomethyl ether (EGM) and deionized water were worked as solvent, pore-forming agent and coagulation bath, respectively. The effects of blending ratio on membrane structure, water contact angle, porosity, pure water flux, BSA rejection rate and antifouling property were investigated. The results showed that the surface contact angle of blending membrane was reduced, the hydrophilicity was enhanced, the pure water flux was increased, and the hydrophilicity and the antifouling ability of the blending membranes were significantly improved with the increase of SPSF mass ratiosince the original neutral amines and sulphonic acid has been changed into corresponding ammonium salts and sulphonates after blending. It was further revealed that the morphology and structure of SPSF/TB blending membrane were completely changed into a gradient sponge pore structurewith the increase of SPSF mass ratio. Especially, the polymer crosslinkedshowed a unique network structuredue to the formation of organic polymer salts at a larger blending ratio. The pure water flux (JWC) and the pure flux recovery rate (FRR) of SPSF/TB3-15reached 274.92~343.21L/(m2·h) (operating pressure of 0.1MPa) and 61.11%~67.45%, respectively, increased by 42.88%~78.37% and 67.4%~84.8% compared with pure TB membrane. The oil-bearing wastewaterrejection of SPSF/TB5 reached more than 98.52%, the water flux and the FRR reached 199.1L/(m2·h), and 61.6% after 3 cycles, respectively under the optimum conditions.
Ahmad N A, Leo C P, Ahmad A L, et al. Membranes with great hydrophobicity:A review on preparation and characterization[J]. Separation & Purification Methods, 2015,44(2):109-134.
[2]
苗瑞吴,公政,王磊,等.超滤膜材料对SiO2-有机物膜污染行为的影响[J]. 中国环境科学, 2019,39(4):1511-1515. Gong Z, Wang L, Wang P, et al. The effect of ultrafiltration membrane materials on the combined fouling behavior of SiO2-organic coexist foulants[J]. China Environmental Science, 2019,39(4):1511-1515.
[3]
Kang G, Cao Y. Application and modification of poly(vinylidene fluoride) (PVDF) membranes-A review[J]. Journal of Membrane Science, 2014,463:145-165.
[4]
Lang W Z, Xu Z, Yang H, et al. Preparation and characterization of PVDF-PFSA blend hollow fiber UF membrane[J]. Journal of Membrane Science, 2007,288(1):123-131.
[5]
Liu T Y, Lin W C, Huang L Y, et al. Surface characteristics and hemocompatibility of PAN/PVDF blend membranes[J]. Polymers for Advanced Technologies, 2005,16(5):413-419.
[6]
Wang Z, Lu Y W, Wang S M. Study on the preparation and characteristics of PVDF/CA blend ultrafiltration membrane[J]. Membrane Science & Technology, 2002,22(6):4-8.
[7]
Wang X, Changfa X, Hailiang L, et al. A study on fabrication of PVDF-HFP/PTFE blend membranes with controllable and bicontinuous structure for highly effective water-in-oil emulsion separation[J]. Rsc Advances, 2018,8(49):27754-27762.
[8]
孙漓青,钱英.聚偏氟乙烯/磺化聚砜共混相容性及超滤膜研究[J]. 膜科学与技术, 2001,21(2):1-5. Sun L Q, Qian Y, Liu S X, et al. Study of polyvinylidene difluoride sulfonate polysulphone co-blend ultrafiltration membrane[J]. Membrane Science and Technology, 2001,21(2):1-5.
[9]
李继定,薛娟琴,王森,等.氧化石墨烯/聚偏氟乙烯杂化超滤膜处理乳化含油废水的研究[J]. 膜科学与技术, 2017,37(5):28-35. Xue J Q, Wang S, Li J D, et al. Treatment of emulsified oily wastewater using graphene oxide/polyvinylidene fluoride hybridized ultrafiltration membrane[J]. Membrane Science and Technology, 2017,37(5):28-35.
[10]
步肖曼,张守海,薛仁东,等.聚醚砜与杂萘联苯共聚醚砜共混超滤膜的制备[J]. 膜科学与技术, 2018,38(6):60-66. Bu X M, Zhang S H, Xue R D, et al. Preparation of poly(ether sulfone)/copoly (phthalazinone biphenyl ether sulfone)blend ultrafiltration membranes[J]. Membrane Science and Technology,2018,38(6):60-66.
[11]
Sajitha C J, Mohan D. Studies on cellulose acetate arboxylate dpolysulfone blend ultrafiltration membranes. III[J]. Journal of Applied Polymer Science, 2010,97(3):976-988.
[12]
续曙光,李静,刘忠洲,等.聚砜-磺化聚砜共混超滤膜的研究[J]. 环境化学, 1993,(6):468-472. Xu S G, Li J, Liu Z Z, et al. Study on blend ultrafiltration membrane of the polysulfone and sulfonated polysulfone[J]. Environmental Chemistry, 1993,(6):468-472.
[13]
张宇峰,王薇梁朝霞.磺化聚砜在聚醚砜膜亲水改性中的制备与表征[J]. 高分子材料科学与工程, 2016,32(4):153-158. Wang W, Liang Z X, Zhang Y F. Preparation and characterization of hydrophilic modification of polyether sulfone membrane by the additive of sulfonated polysulfone[J]. Polymer Materials Science and Engineering, 2016,32(4):153-158.
[14]
Lei Z, Cui Z, Hu M, et al. Preparation of PES/SPSf blend ultrafiltration membranes with high performance via H2O-induced gelation phase separation[J]. Journal of Membrane Science, 2017,540:136-145.
[15]
Li S, Cui Z, Zhang L, et al. The effect of sulfonated polysulfone on the compatibility and structure of polyethersulfone-based blend membranes[J]. Journal of Membrane Science, 2016,513:1-11.
[16]
Jin J, Wang Z, Ren H, et al. Carbon molecular sieve membranes derived from Tröger's base microporous polyimide for gas separation[J]. Chemsuschem, 2018,11(5):148-155.
[17]
Xu Z, Liao J, Tang H, et al. Preparation and antifouling property improvement of Tröger's base polymer ultrafiltration membrane[J]. Journal of Membrane Science, 2018,561:59-68.
[18]
Carta M, Croad M, Jansen J C, et al. Synthesis of cardo-polymers using Tröger's base formation[J]. Polymer Chemistry, 2014,5(18):5267-5272.
[19]
Zhu L P, Dong H, Wei X, et al. Tethering hydrophilic polymer brushes onto PPESK membranes via surface-initiated atom transfer radical polymerization[J]. Journal of Membrane Science, 2008,320(1):407-415.
[20]
Zeng M, Fang Z, Xu C. Effect of compatibility on the structure of the microporous membrane prepared by selective dissolution of chitosan/synthetic polymer blend membrane[J]. Journal of Membrane Science, 2004,230(1):175-181.
[21]
赵宝宝,李诗文,付振刚,等.PSF/SPES共混相容性及其对膜形态结构和性能的影响规律[J]. 膜科学与技术, 2015,35(5):6-12. Zhao B B, Li S W, Fu Z G, et al. The compatibility of PSf and SPES blends and its effects on the structure and performance of blend membrane[J]. Membrane Science and Technology, 2015,35(5):6-12.
[22]
Chenga L, Youngb T, Youa W. Formation of crystalline EVAL membranes by controlled mass transfer process in water-DMSOEVAL copolymer systems[J]. Journal of Membrane Science, 1998, 145(1):77-90.
[23]
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]. Journal of Membrane Science, 2014,468:172-183.
[24]
Chen W, Wei M J, Wang Y, et al. Advanced ultrafiltration membranes by leveraging microphase separation in macrophase separation of amphiphilic polysulfone block colymers[J]. Journal of Membrane Science, 2017,525:342-348.
[25]
Sharma N, Purkait M K. Impact of synthesized amino alcohol plasticizer on the morphology and hydrophilicity of polysulfone ultrafiltration membrane[J]. Journal of Membrane Science, 2017, 522:202-215.
[26]
Kim H J, Fouda A E, Jonasson K. In situ study on kinetic behavior during asymmetric membrane formation via phase inversion process using Raman spectroscopy[J]. Journal of Applied Polymer Science, 2015,75(1):135-141.
[27]
Di S, Jia X, Fu Y, et al. Polysulfone/sulfonated polysulfone alloy membranes with an improved performance in processing mariculture wastewater[J]. Chemical Engineering Journal, 2016,304:882-889.
[28]
Huang, Shuhsien, Hsu, et al. Effect of chemical structures of amines on physicochemical properties of active layers and dehydration of isopropanol through interfacially polymerized thin-film composite membranes[J]. Journal of Membrane Science, 2008,307(1):73-81.
[29]
Wijmans J G, Baaij J P B, Smolders C A. The mechanism of formation of microporous or skinned membranes produced by immersion precipitation[J]. Journal of Membrane Science, 1983, 14(3):263-274.
[30]
Bowen W R, Doneva T A, Yin H B. Polysulfone-sulfonated poly(ether ether) ketone blend membranes:systematic synthesis and characterization[J]. Journal of Membrane Science, 2001,181(2):253-263.
[31]
Mahendra K, Ulbricht M. Low fouling negatively charged hybrid ultrafiltration membranes for protein separation from sulfonated poly (arylene ether sulfone) block copolymer and functionalized multiwalled carbon nanotubes[J]. Separation & Purification Technology, 2014,127(127):181-191.
[32]
ZhaoY H, Wee, et al. Highly hydrophilic and low-protein-fouling polypropylene membrane prepared by surface modification with sulfobetaine-based zwitterionic polymer through a combined surface polymerization method[J]. Journal of Membrane Science, 2010, 362(1):326-333.
[33]
Chinpa W, Quémener D, Bèche E, et al. Preparation of poly (etherimide) based ultrafiltration membrane with low fouling property by surface modification with poly (ethylene glycol)[J]. Journal of Membrane Science, 2018,365(1):89-97.
[34]
Hao J, Mccloskey B D, Sagle A C, et al. Preparation and characterization of crosslinked poly (ethylene glycol) diacrylate hydrogels as fouling-resistant membrane coating materials[J]. Journal of Membrane Science, 2009,330(1):180-188.
