摘要
通过悬浮聚合和超交联两步法合成了具有介孔结构的改性聚苯乙烯微球用作血液净化材料。首先采用悬浮聚合法制备了亲水改性的苯乙烯-马来酸酐共聚微球(MPPS),然后将MPPS微球以二氯甲烷为溶剂、无水氯化铝为催化剂进行后交联处理,制备了含有介孔结构的、具有较高比表面积的聚苯乙烯(HCLPS)多孔微球。采用比表面积测试、扫描电子显微镜、傅里叶红外光谱、X射线光电子能谱等仪器分析表征了微球的结构和形貌,并测试了HCLPS微球的吸水性和戊巴比妥钠吸附性能。结果表明,超交联反应可以显著提高微球的比表面积,并且随着马来酸酐(MAH)含量增加,微球的吸水性和戊巴比妥钠吸附性能提高;当MAH含量为20%(质量分数,下同)时HCLPS微球的戊巴比妥钠吸附率为91.90%。
The polystyrene(PS) microspheres with a micro-mesoporous structure were synthesized by suspension copolymerization using maleic anhydride(MAH) as a comonomer, followed by a hyper-crosslinking reaction using dichloromethane as a crosslinking agent and anhydrous aluminum chloride as a catalyst. The resultant PS microspheres were further characterized to determine their chemical structure and morphology by specific surface area test, scanning electron microscopy, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Moreover, the water absorption and pentobarbital adsorption performance of the microspheres were measured. The results indicated that the specific surface area of the microspheres was significantly improved by the hyper-crosslinking reaction. The water absorption and pentobarbitol adsorption performance were also enhanced with an increase of MAH content. The microspheres achieved a maximum pentobarbital adsorption capacity of 91.90 % at the MAH content of 20 wt%.
引文
[1] CHANG T M. Artificial Cells in Immobilization Biotechnology[J]. Biomaterials, Artificial Cells, and Immobilization Biotechnology, 1992, 20(5):1 121.
[2] OUYANG D W, LIANG L Q. Research Progress of Application of Continuous Blood Purification for Patients with Multiple Organ Dysfuncation Syndrome[J]. Medical Recapitulate, 2013, 19(3):476-479.
[3] YATZIDIS H. A Convenient Haemoperfusion Micro-apparatus over Charcoal for the Treatment of Endogenous and Exogenous Intoxications. Its Use as an Effective Artificial Kidney[J]Proc Eur Dial Transplant Assoc, 1964, 1: 83-87.
[4] KUSHI H, MIKI T, SAKAGAMI Y, et al. Early Hemoperfusion With a Polymyxin B Column Improves Gastric Intramucosal pH in Sepsis[J]. Therapeutic Apheresis and Dialysis, 2010, 12(4):278-284.
[5] 何炳林,史作清.大孔离子交换树脂及新型吸附树脂的结构与性能[J].高分子通报, 2005(04):13-19. HE B L, SHI Z Q. Structure and Properties of Macroporous Ion Exchange Resin and Novel Adsorption Resin[J]. Polymer Bulletin, 2005(4):13-19.
[6] LUZ C T L, COUTINHO F M B. The Influence of the Diluent System on the Porous Structure Formation of Copolymers Based on 2-Vinylpyridine and Divinylbenzene. Diluent System III. Heptane/Methylethyl Ketone[J]. Journal of Applied Polymer Science, 2010, 91(1):666-669.
[7] 王海志.高比面积吸附树脂的合成及其应用[D]. 长春: 长春工业大学,2011.
[8] YANG Y, TAN B, WOOD C D. Solution-processable Hypercrosslinked Polymers by Low Cost Strategies: A Promising Platform for Gas Storage and Separation[J]. Journal of Materials Chemistry A, 2016, 4(39): 15 072-15 080.
[9] YANG X, TAN L, XIA L, et al. Hierarchical Porous Polystyrene Monoliths from PolyHIPE[J]. Macromolecular Rapid Communications, 2015, 36(17): 1 553-1 558.
[10] 郑从光. 低氯含量超高交联聚苯乙烯的制备及其性能研究[D]. 长沙: 湖南师范大学, 2014.
[11] 张兴英,李齐方.高分子科学实验[M].第二版,北京:化学工业出版社,2016:86-88.
[12] TAN L, TAN B. Hypercrosslinked Porous Polymer Materials: Design, Synthesis, and Applications[J]. Chemical Society Reviews, 2017, 46(11):3 322.
[13] 叶晓燕,刘贻声,张文,等.中分子物质吸附性能在血液灌流器检测中的必要性及其检测方法的探讨[J].中国医疗器械信息, 2012,18(4):60-62. YE X Y, LIU Y S, ZHANGW, et al. The Adsorption of Middle Molecular Substances in the Blood Perfusion in the Detection of Necessity and the Discussion on the Detection Methods[J]. China Medical Device Information, 2012,18(4):60-62.
[14] BARBETTA A, CAMERON N R. Morphology and Surface Area of Emulsion-derived (PolyHIPE) Solid Foams Prepared with Oil-phase Soluble Porogenic Solvents: Three-component Surfactant System[J]. Macromolecules, 2004, 37(9): 3 202-3 213.
[15] LI B, GONG R, WANG W, et al. A New Strategy to Microporous Polymers: Knitting Rigid Aromatic Building Blocks by External Cross-Linker[J]. Macromolecules, 2011, 44(8): 2 410-2 414.
[16] GERMAIN J, FRéCHET J M J, SVEC F. Hypercrosslinked Polyanilines with Nanoporous Structure and High Surface Area: Potential Adsorbents for Hydrogen Storage[J]. Journal of Materials Chemistry, 2007, 17(47): 4 989-4 997.
[17] ERRAHALI M, GATTI G, TEI L, et al. Microporous Hyper-cross-linked Aromatic Polymers Designed for Methane and Carbon Dioxide Adsorption[J]. The Journal of Physical Chemistry C, 2014, 118(49): 28 699-28 710.
[18] 滕越. 柴达木盆地石炭系页岩吸水——饱水特性研究[D]. 北京:中国地质大学, 2017.
[19] HE J, TO J W F, PSARRAS P C, et al. Tunable Polyaniline-Based Porous Carbon with Ultrahigh Surface Area for CO2 Capture at Elevated Pressure[J]. Advanced Energy Materials, 2016, 6(14): 1 502 491
[20] BYUN J, PATEL H A, THIRION D, et al. Charge-specific Size-dependent Separation of Water-soluble Organic Molecules by Fluorinated Nanoporous Networks[J]. Nature communications, 2016, 7: 13 377.
[21] DUAN C, DU Z, ZOU W, et al. Construction of Nitrogen-Containing Hierarchical Porous Polymers and Its Application on Carbon Dioxide Capturing[J]. Industrial & Engineering Chemistry Research, 2018, 57(15): 5 291-5 300.