摘要
聚砜的多孔材料由于其优越的热性能,电性能和耐候性,在生物医药,燃料电池等领域内都有很好的用途。然而,用现有的方法所制备的多孔材料,往往只有较低的孔隙率并且只能做成薄膜状的材料。本论文采用浓乳液法来制备聚砜的多孔材料,利用这种方法能够制备高孔隙率并且具有通孔结构的大块的多孔材料。在制备的过程中,首先制备的是由聚砜的氯仿溶液与去离子水组成的“传统”乳液。在溶剂氯仿挥发之后,这种“传统”乳液逐渐转化成了浓乳液。在将浓乳液中的水分去除之后,制备成具有高孔隙率通孔结构的聚砜的多孔材料。本论文主要合成了氨基化的聚砜,这种双亲性的聚合物能很好的使聚砜的乳液稳定；探索了影响多孔材料孔结构的因素,如：水油比的影响、乳化剂的影响、以及溶剂挥发速率的影响；在此基础上提出了多孔材料形成的机理。
A methodology for preparing porous polysulfone (PSF) monolith via concentrated emulsion templating was proposed. A regular emulsion was first prepared using a solution of PSF in chloroform as the continuous phase and deionized water as the dispersed one. Amintated polysulfone was employed as a macromolecular surfactant. After the emulsion was formed, the liquid species in the emulsion was allowed to be evaporated. The solvent chloroform was first removed and the emulsion was transformed to a concentrated emulsion. Further removing the aqueous species, a porous PSF monolith was obtained. The effects of chloroform and water fractions, the nature and loading of the macromolecular surfactant, the evaporating temperature on the pore structure were investigated. Controlled porous structure with different pore size and porosity could be obtained through the method.
引文
[1]Tanev PT, Chibwe M, Pinnavaia TJ. Titanium-containing mesoporous molecular-sieves for catalytic-oxidation of aromatic-compounds. Nature 1994;368(6469):321.
[2]Corma A, Davis ME. Issues in the synthesis of crystalline molecular sieves:towards the crystallization of low framework-density structures. ChemPhysChem 2004;5(3):304.
[3]Davis ME. Ordered porous materials for emerging applications. Nature 2002;417(6891):813.
[4]Joannopoulos JD, Meade RD, Winn JN. Photonic crystals:molding the flow of light; 1995.
[5]Xia YN, Gates B, Yin YD, Lu Y. Monodispersed colloidal spheres:old materials with new applications. Adv Mater 2000;12(10):693.
[6]Russell PSJ. Joannopoulos JD, Meade RD, Winn, JN. Photonic crystals:molding the flow of light.. Nature 1996;381(6580):290.
[7]Urbas A, Sharp R, Fink Y, Thomas EL, Xenidou M, Fetters LJ. Tunable block copolymer/homopolymer photonic crystals. Adv Mater 2000; 12(11):812.
[8]Campbell M, Sharp DN, Harrison MT, Denning RG, Turberfield AJ. abrication of photonic crystals for the visible spectrum by holographic lithography. Nature 2000;404(6773):53.
[9]Akolekar DB, Hind AR, Bhargava SK. Synthesis of macro-, meso-, and microporous carbons from natural and synthetic sources, and their application as adsorbents for the removal of quaternary ammonium compounds from aqueous solution. J Colloid Interface Sci1998;199(1):92.
[10]Lewandowski K, Murer P, Svec F, Frechet JMJ. The design of chiral separation media using monodisperse functionalized macroporous beads:effects of polymer matrix, tether, and linkage chemistry. Anal Chem 1998;70(8):1629.
[11]Xie SF, Svec F, Frechet JMJ. Rigid porous polyacrylamide-based monolithic columns containing butyl methacrylate as a separation medium for the rapid hydrophobic interaction chromatography of proteins. J Chromatogr A 1997;775(1-2):65
[12]TennikovMB,GazdinaNV, Tennikova TB, Svec F. Effect of porous structure of macroporous polymer supports on resolution in high-performance membrane chromatography of proteins. J Chromatogr A 1998;798(1-2):55.
[13]Palm A, Novotny MV. Macroporous polyacrylamide poly(ethylene glycol) matrixes as stationary phases in capillary electrochromatography. Anal Chem 1997;69(22):4499.
[14]Busby W, Cameron NR, Jahoda ABC. Tissue engineering matrixes by emulsion templating. Polym Int 2002;51(10):871.
[15]Bancel S, Hu WS. Confocal laser scanning microscopy examination of cell distribution in macroporous microcarriers. Biotechnol Prog 1996; 12 (3):398.
[16]Schugens C, Maquet V, Grandfils C, Jerome R, Teyssie P. Biodegradable and macroporous polylactide implants for cell transplantation.1. Preparation of macroporous polylactide supports by solid-liquid phase separation. Polymer 1996;37(6):1027.
[17]Nishikawa T, Nishida J, Ookura R, Nishimura SI,Wada S, Karino T, et al. Honeycomb-patterned thin films of amphiphilic polymers as cell culture substrates. Mater Sci Eng C Biomim Supramol Syst 1999;8-9:495.
[18]Nishikawa T, Nishida J, Ookura R, Nishimura SI,Wada S, Karino T, et al. Mesoscopic patterning of cell adhesive substrates as novel biofunctional interfaces. Mater Sci Eng C Biomim Supramol Syst 1999;10(1-2):141.
[19]van Noort D, Rani R, Mandenius CF. Improving the sensitivity of a quartz crystal microbalance for biosensing by using porous gold. Mikrochim Acta 2001; 136(1-2):49.
[20]van Noort D, Mandenius CF. Porous gold surfaces for biosensor applications. Biosens Bioelectron 2000;15(3-4):203.
[21]Yabu H, Takebayashi M, Tanaka M, Shimomura M. Superhydrophobic and lipophobic properties of self-organized honeycomb and pincushion structures. Langmuir 2005;21(8):3235.
[22]Park M, Harrison C, Chaikin PM, Register RA, Adamson DH. Block copolymer lithography:periodic arrays of similar to 10(11) holes in 1 square centimeter. Science 1997;276(5317):1401.
[23]Mansky P, Harrison CK, Chaikin PM, Register RA, Yao N. Nanolithographic templates from diblock copolymer thin films. Appl Phys Lett 1996;68(18):2586.
[24]侯文华,徐林,颜其洁等.具有超大通道结构的介孔氧化硅柱层状钛酸的合成和催化应用初探[J].无机化学学报,2002.18(7)：744-747
[25]Estermann M, Mccusker L B, Baerlocher C, et al. A synthetic gallophosphate molecular sieve with a 20-tetrahedral-atom pore opening[J]. Nature,1991.352:320-323
[26]Imhof A, Pine DJ. Uniform macroporous ceramics and plastics by emulsion templating. Adv Mater 1998; 10(9):697.
[27]翟尚儒,蒲敏,张晔等.纯硅MCM-48的合成研究[J].无机化学学报,2002.18(11)：1081-1085
[28]J Wang, Y Xu, L Zhu, J Li, B Zhu; Amphiphilic ABA copolymers used for surface modification of polysulfone membranes, Part 1:Molecular design, synthesis, and characterization[J] Polymer,2008,48,3256-3264
[29]Srinivasarao, M.; Collings, D.; Philips, A.; Patel, S. Science 2001,292,79.
[30]Boer, B.; Stalmach, U.; Nijland, H.; Hadziioannou, G. Adv Mater 2000,12,1581.
[31]Yabu, H.; Tanaka, M.; Ijiro, K.; Shimomura, M. Langmuir 2003,19,6297.
[32]Lissant K J. Geometry of high-inter-phase-ratio emulsions[J]. J. Colloid Interface Sci., 1966.22:462-468
[33]Solans C, Pons R, Kunieda H. Gel emusion-relationship between phase behavior and formation[M]. In:Binks BP, editor. Modern aspect of emulsion science.UK:The Royal Society of Chemistry,1998.20:367-394
[34]Hoffman H. Large shells in collective nuclear dynamics[J]. Adv Colloid Interface Sci., 1990.32:123-129
[35]Ruckenstein E, Kim K J. Polymerization in gel-like emulsions[J]. J Appl Polym Sci., 1988,36(4):907-923
[36]X Li, C Zhang, Z Du, H Li, Preparation of hydrophilic/hydrophobic porous materials[J] J Colloid and Interface science,2008,323,120-125
[37]J Wang, C Zhang, Z Du, A Xiang, H Li, Formation of porous epoxy monolith via concentrated emulsion polymerization, J Colloid and Interface science,2008,325,453-458
[38]J Li, Z Du, H Li, C Zhang, Porous epoxy monolith prepared via chemically induced phase separation, Polymer,2009,50,1526-1532
[39]Barbetta A, Carnachan R J. Smith K H. Porous polymers by emulsion templating[J]. Macromol Symp,2005.226:203-211
[40]Cameron N R. Sherrington D C. Synthesis and characterization of poly (aryl ether sulfone) polyHIPE materials[J]. Macromolecules,1997,30:5860-5869
[41]常海涛,鲁在君.油包水高内相比乳液模板法制备聚苯乙烯多孔材料[J].精细与专业化学品,2007.15(9)：17-20
[42]陈素芸,孙国明,姜磊,李楠,李培勇,朱新远,细胞内转运载体超支化聚砜胺及其生物相容性[J]高等学校化学学报,2009,30,825-829
[43]王进,刘瑞泉,王吉德,刘玉星,磺化聚砜质子交换膜在低温常压电化学合成氨中的应用[J],科学通报,2008,53,1032-1035
[44]侯士法.非氟质子传导聚合物膜的制备与性能[J].高分子通报2003(10)：7-16
[45]Manea.CarI11enet.CharacterizationofPolymerblendsofPolyethersulfone /sulfonatedPolysulfoneandPolyethersulfone/sulfonatedPolyetheretherketonefor direetmethanolfueleellapPlieations[J].J.Membr.Sei,2002,206(1-2):443-453.
[46]崔韬聚砜膜的制备及其在垃圾渗滤液处理中的应用2008.12
[47]Nobuhiro Tanaka, Takao Iijima, Wakichi Fukuda, Masao Tomoi, Synthesis and Properties of Interpenetrating Polymer Networks Composed of Epoxy Resins and Polysulphones with Cross-linkable Pendant Vinylbenzyl Groups, Polymer International,1997,47,95-106
[48]Yingfeng Yu, Zhicheng Zhang, Wenjun Gan, Minghai Wang, and Shanjun Li, Effect of Polyethersulfone on the Mechanical and Rheological Properties of Polyetherimide-Modified Epoxy Systems, Ind. Eng. Chem. Res.2003,42,3250-3256
[49]P. A. OYANGUREN,1 B. AIZPURUA,2 M. J. GALANTE.1 C. C. RICCARDI.1 O. D. CORTA'ZAR,3 I. MONDRAGON, Design of the Ultimate Behavior of Tetrafunctional Epoxies Modified with Polysulfone by Controlling Microstructure Development, Journal of Polymer Science:Part B:Polymer Physics,1999,37,2711-2725
[50]Xiaolin Tang, Linxia Zhang, Tao Wang, Yingfeng Yu, Wenjun Gan, Shanjun Li, Hydrodynamic Effect on Secondary Phase Separation in an Epoxy Resin Modified with Polyethersulfone, Macromol. Rapid Commun.2004,25,1419-1424
[51]Krause, B.; Boerrigter, M. E.; van der Vegt, N. F. A.; Strathmann, H.; Wessling, M. J Membrane Sci 2001,187,181.
[52]Krause, B.; Diekmann, K.; van der Vegt, N. F. A.; Wessling, M. Macromolecules 2002,35, 1738.
[53]Krause, B.; Sijbesma, H. J. P.; Munuklu, P.; van der Vegt N. F. A, Wessling, M. Macromolecules 2004,34,8792.
[54]Vandezande, P.; Gevers, L.; Vermant, J.; Martens, J.; Jacobs, P.; Vankelecom, I. Chem Mater 2008,20,3457.
[55]Vandezandel, P.; Gevers, L.; Jacobs, P.; Vankelecom, I. Sep Purif Technol 2009,66,104.
[56]Coleman JN, Khan U, Gun'ko YK. Mechanical reinforcement of polymers using carbon nanotubes. Adv Mater 2006;18(6):689-706.
[57]Zhang M, Gorski W. Electrochemical sensing platform based on the carbon nanotubes/redox mediators-biopolymer system. J Am Chem Soc 2005;127(7):2058-9.
[58]Zhang M, Gorski W. Electrochemical sensing platform based on the carbon nanotubes/redox mediators-biopolymer system. J Am Chem Soc 2005;127(7):2058-9.
[59]Asuri P, Karajanagi SS, Dordick JS, Kane RS. Directed assembly of carbon nanotubes at liquid-liquid interfaces:nanoscale conveyors for interfacial biocatalysis. J Am Chem Soc 2006;128(4):1046-7.
[60]Zhu L, Sun Y, Hess DW, Wong C-P. Well-aligned open-ended carbon nanotube architectures:an approach for device assembly. Nano Lett 2006;6(2):243-7.
[61]Liu YX, Zhang C, Du ZJ, Li CJ, Li Y, Li H, Yang XP. The preparation of multi-walled carbon nanotubes encapsulated by poly(3-acrylaminopropylsiloxane) with silica nanospheres on the polymer surface. Carbon 2008;46:1670-7.
[62]Grzelczak M, Correa-Duarte MA, Liz-Marzan LM. Carbon nanotubes encapsulated in wormlike hollow silica shells. Small 2006;2(10):1174-7
[63]Kaur S, Ajayan PM, Kane RS. Design and characterization of three-dimensional carbon nanotubes foams. J Phys Chem B 2006;110(42):21377-80.
[64]Zhou W, Zhang Y, Li X, Yuan S, Jin Z, Xu J, et al. Preferential growth of single-walled carbon nanotubes on silica spheres by chemical vapor deposition. J Phys Chem B 2005;109(15):6963-7.
[65]Agrawal S, Kumar A, Frederick MJ, Ramanath G. Hybrid microstructures from aligned carbon nanotubes and silica particles. Small 2005; 1(8-9):823-6.
[66]Sainsbury T, Fitzmaurice D. Templated assembly of semiconductor and insulator nanoparticles at the surface of covalently modified multiwalled carbon nanotubes. Chem Mater 2004;16(19):3780-90.
[67]Zhang W, Phang IY, Shen L, Chow SY, Liu T. Polymer nanocomposites using urchin-shaped carbon nanotubes-silica hybrids as reinforcing fillers. Macromol Rapid Commun 2004;25(21):1860-4.
[68]Correa-Duarte MA, Kosiorek A, Kandulski W, Giersig M, Liz-Marzan LM. Layer-by-layer assembly of multiwall carbon nanotubes on spherical colloids. Chem Mater 2005;17(12):3268-72.
[69]Olek M, Kempa K, Jurga S, Giersig M. Nanomechanical properties of silica-coated multiwall carbon nanotubespoly(methyl methacrylate) composites. Langmuir 2005;21(7):3146-52.
[70]Bottini M, Tautz L, Huynh H, Monosov E, Bottini N, Dawson MI, et al. Covalent decoration of multi-walled carbon nanotubes with silica nanoparticles. Chem Commun 2005;5(6):758-60.
[71]Li X, Liu Y, Fu L, Cao L, Wei D, Wang Y, et al. Synthesis and device integration of carbon nanotubes/silica core-shell nanowires. J Phys Chem C 2007;111(21):7661-5.
[72]Santra S, Zhang P, Wang K, Tapec R, Tan W. Conjugation of biomolecules with luminophore-doped silica nanoparticles for photostable biomarkers. Anal Chem 2001;73(20):4988-93.
[73]Liu YX, Du ZJ, Li Y, Zhang C, Li CJ, Yang XP, et al. Surface covalent encapsulation of multiwalled carbon nanotubes with poly(acryloyl chloride) grafted poly(ethylene glycol). J Polym Sci Pol Chem 2006;44(23):6880-7.
[74]Liu YX, Du ZJ, Li Y, Zhang C, Li CJ, Li H. Covalent functionalization of multiwalled carbon nanotubes with poly(acrylic acid). Chin J Chem 2006;24(4):563-8.