凝固浴组成对聚丙烯腈基中空中孔纤维结构和性能的影响
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摘要
中空中孔纤维作为一种新型材料,兼具中空和介孔的特性,对拓展中空纤维中大分子发挥作用的应用领域具有重要的影响。本文采用湿法纺丝相分离的方法成功制备了中空中孔纤维,并且采用扫描电镜、氮气物理吸附仪、热重分析仪等仪器对纤维结构和性能进行了表征。通过控制凝固浴组成,实现了对纤维直径和孔隙结构的调控,凝固浴中二甲基亚砜浓度的增加,纤维直径和孔隙率先减小后增加,壁上的介孔向小尺寸方向移动。600℃炭化时纤维的炭收率均大于40%,有望将其加工成为炭纤维,为中空中孔炭纤维的制备提供实验支撑。
Combining the advantages of hollow and mesoporous structures,hollow mesoporous fibers have great potential in the adsorption of macromolecules.Such fibers were fabricated by a wet-spinning method from a polymer mixture of polyacrylonitrile and alkali lignin.The effect of the composition of the solution in the coagulation bath on the microstructures of the hollow mesoporous fibers produced was investigated by SEM,TGA and nitrogen adsorption.Results indicate that the diameter and pore structure of the fibers were changed by the composition of the solution in the coagulation bath.By increasing the concentration of dimethyl sulfoxide,the average pore size of the fibers decreased from 45.3 to 24.4 nm while the outer diameter and porosity reached minima of 137.5 μm and 88.7%,respectively while the wall thickness reached a maximum of 20.3 μm.The fibers can be processed into hollow mesoporous carbon fibers because of their high carbon yield of 40%.
Combining the advantages of hollow and mesoporous structures,hollow mesoporous fibers have great potential in the adsorption of macromolecules.Such fibers were fabricated by a wet-spinning method from a polymer mixture of polyacrylonitrile and alkali lignin.The effect of the composition of the solution in the coagulation bath on the microstructures of the hollow mesoporous fibers produced was investigated by SEM,TGA and nitrogen adsorption.Results indicate that the diameter and pore structure of the fibers were changed by the composition of the solution in the coagulation bath.By increasing the concentration of dimethyl sulfoxide,the average pore size of the fibers decreased from 45.3 to 24.4 nm while the outer diameter and porosity reached minima of 137.5 μm and 88.7%,respectively while the wall thickness reached a maximum of 20.3 μm.The fibers can be processed into hollow mesoporous carbon fibers because of their high carbon yield of 40%.
引文
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[20]Chou W L,Yu D G,Yang M C.Influence of Coagulant Temperature and On-Line Draw ing on the Mechanical Properties and Permeation Performance of Cellulose Acetate Hollow Fibers[J].Journal of Polymer Research,2005,12(3):219-259.
[21]Knudsen J P.The influence of coagulation variables on the structure and physical properties of an acrylic Fiber[J].Textile Research Journal,1963,33(1):13-20.
[22]Sobhanipour P,Cheraghi R,Volinsky A A.Thermoporometry study of coagulation bath temperature effect on polyacrylonitrile fibers morphology[J].Thermochim Acta,2011,518(1-2):101-106.
[2]Feng C Y,Khulbe K C,Matsuura T,et al.Recent progresses in polymeric hollow fiber membrane preparation,characterization and applications[J].Separation and Purification Technology,2013,111:43-71.
[3]Peng N,Widjojo N,Sukitpaneenit P,et al.Evolution of polymeric hollow fibers as sustainable technologies:Past,present,and future[J].Progress in Polymer Science,2012,37(10):1401-1424.
[4]Hou D,Wang J,Qu D,et al.Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation[J].Separation and Purification Technology,2009,69(1):78-86.
[5]Rahbari-sisakht M,Ismail A F,Matsuura T.Development of asymmetric polysulfone hollow fiber membrane contactor for CO2absorption[J].Separation and Purification Technology,2012,86(2):15-20.
[6]Ovcharova A,Vasilevsky V,Borisov I,et al.Polysulfone porous hollow fiber membranes for ethylene-ethane separation in gasliquid membrane contactor[J].Separation and Purification Technology,2017,183(1):62-72.
[7]王胤,李君华,黄钟扬,等.介孔分子筛合成及应用的研究进展[J].天津化工,2016,30(04):1-4.(Wang Y,Li J H,Huang Z Y,et al.Research progress in synthsis and applications of mesoporous molecular sieves[J].Tianjin Chemical Industry,2016,30(4):1-4.)
[8]祖新月,所艳华,汪颖军.硅基介孔材料MCM-48的合成、改性及催化领域应用的研究进展[J].硅酸盐通报,2016,35(01):160-166.(Zu X Y,Suo Y Y,Wang Y J.Progress in synthesis,modification and application in coctalysis of silicon-based mesoporous materials MCM-48[J].Bulletin of the Chinese Ceramic Society,2016,35(01):160-166.)
[9]朱玲.功能化介孔硅纳米材料在蛋白质吸附分离中的应用[D].兰州大学,2012.(Zhu L.Application of functionalized mesoporous silica nanoparticles on adsorption and separation of proteins[D].Lanzhou University,2012.)
[10]宗洁.介孔二氧化硅微球纳米反应器的设计及其产物的研究[D].华东理工大学,2013.(Zong J.Fabrication of mesoporous silica spheres based nanoreactors and study of their products[D].East China University of Science and Technology,2013.)
[11]Li W,Ge X,Zhang H,et al.Hollow mesoporous SiO2sphere nanoarchitectures with encapsulated silver nanoparticles for catalytic reduction of 4-nitrophenol[J].Inorganic Chemistry Frontiers,2016,3(5):663-670.
[12]Zhang B,Lu C X,Liu Y D,et al.Wet spun polyacrylontrilebased hollow fibers by blending with alkali lignin[J].Polymer,2018,149:294-304.
[13]Kune-woo L B K S,Suk-tea N,Myeong-jin H.Trade-off between thermodynamic enhancement and kinetic hindrance during phase inversion in the preparation of polysulfone membranes[J].Desalination,2003,159(2):89-96.
[14]Arbab S,Noorpanah P,Mohammadi N,et al.Exploring the effects of non-solvent concentration,jet-stretching and hotdraw ing on microstructure formation of poly(acrylonitrile)fibers during wet-spinning[J].Journal of Polymer Research,2011,18(6):1343-1351.
[15]Yu D G,Chou W L,Yang M C.Effect of bore liquid temperature and dope concentration on mechanical properties and permeation performance of polyacrylonitrile hollow fibers[J].Separation and Purification Technology,2006,51(1):1-9.
[16]李人杰,吕春祥,李永红,等.水洗条件对PAN水洗丝条结构和力学性能的影响[J].化工新型材料,2009,37(03):80-2.(Li R J,Lu C X,Li Y H,et al.Effect of the water washing technology on the structure and mechanical properties of PANw ater w ashing fiber[J].New Chemical Materials,2009,37(03):80-82.)
[17]Wang Y X,Wang C G,Yu M J.Effects of different coagulation conditions on polyacrylonitrile fibers wet spun in a system of dimethylsulphoxide and water[J].Journal of Applied Polymer Science,2007,104(6):3723-3729.
[18]Dong X G,Wang C G,Bai Y J,et al.Effect of DMSO/H2Ocoagulation bath on the structure and property of polyacrylonitrile fibers during wet-spinning[J].Journal of Applied Polymer Science,2007,105(3):1221-1227.
[19]Peng G Q,Zhang X H,Wen Y F,et al.Effect of coagulation bath DMSO concentration on the structure and properties of polyacrylonitrile(PAN)nascent fibers during wet-spinning[J].Journal of Macromolecular Science B,2008,47(6):1130-1141.
[20]Chou W L,Yu D G,Yang M C.Influence of Coagulant Temperature and On-Line Draw ing on the Mechanical Properties and Permeation Performance of Cellulose Acetate Hollow Fibers[J].Journal of Polymer Research,2005,12(3):219-259.
[21]Knudsen J P.The influence of coagulation variables on the structure and physical properties of an acrylic Fiber[J].Textile Research Journal,1963,33(1):13-20.
[22]Sobhanipour P,Cheraghi R,Volinsky A A.Thermoporometry study of coagulation bath temperature effect on polyacrylonitrile fibers morphology[J].Thermochim Acta,2011,518(1-2):101-106.
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