| 包建民,闫志英,李优鑫.微米级多孔聚苯乙烯-二乙烯苯微球的制备、改性及应用综述[J].材料导报,2018,32(17):3060-3067 |
| 微米级多孔聚苯乙烯-二乙烯苯微球的制备、改性及应用综述 |
| Microporous Poly(Styrene-Divinylbenzene) Microspheres:Preparation, Modification and Application |
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| DOI：10.11896/j.issn.1005-023X.2018.17.019 |
| 中文关键词: 微米级多孔聚苯乙烯-二乙烯苯微球 悬浮聚合 种子溶胀 沉淀聚合 微工程乳化 功能化改性 |
| 英文关键词: microporous poly(styrene-divinylbenzene) microspheres, suspension polymerization, seed swelling, precipitation polymerization, microengineering emulsification, functionalization modification |
| 基金项目:国家自然科学基金(21375093;21605112)；天津市应用基础与前沿技术研究计划青年项目(15JCQNJC43200) |
| 作者 | 单位 | E-mail | | 包建民 | 天津大学药物科学与技术学院,天津市现代药物传递及功能高效化重点实验室,天津化学化工协同创新中心,天津 300072 | bao@tju.edu.cn,lyx@tju.edu.cn | | 闫志英 | 天津大学药物科学与技术学院,天津市现代药物传递及功能高效化重点实验室,天津化学化工协同创新中心,天津 300072 | | | 李优鑫 | 天津大学药物科学与技术学院,天津市现代药物传递及功能高效化重点实验室,天津化学化工协同创新中心,天津 300072 | bao@tju.edu.cn,lyx@tju.edu.cn |
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| 中文摘要: |
| 微米级多孔聚合物微球作为一种新型功能材料,是目前高分子材料领域的一大研究热点。微球粒径通常在1 μm至数百微米,干燥状态下内部有几埃甚至几千埃的孔隙,具有球形度好、比表面积大、骨架密度低、吸附性强、力学强度高、与不同极性的有机溶剂兼容性好等诸多优点,在生物医学、分析化学、环境保护、催化剂载体以及电子产品等领域中有十分广阔的应用前景。其中多孔聚苯乙烯-二乙烯苯微球除了具有高分子微球的一般特点外,还有物理及化学稳定性好、热稳定性好、生产成本低、工业应用前景广等优点,同时微球的苯环反应活性高,易于进行一系列的功能化反应,从而扩大其应用领域。基于上述优点,多孔聚苯乙烯-二乙烯苯微球是目前应用最多的多孔聚合物微球。 广阔的应用前景和市场,使得多孔聚苯乙烯-二乙烯苯微球的制备和功能化成为国内外学者研究的热点,并取得了令人瞩目的发展。在过去的几十年中逐渐出现了多种微球制备方法。悬浮聚合法是制备多孔聚苯乙烯-二乙烯苯微球的传统方法,其操作简单,产物后处理方便,但是得到的微球粒径呈多分散性。种子溶胀法被普遍认为是制备单分散多孔聚苯乙烯-二乙烯苯微球较好的方法,该方法在制备表面功能化、单分散大粒径的聚苯乙烯-二乙烯苯微球方面具有明显优势。沉淀聚合法也可以用来制备单分散的微球,但是该方法制备的微球交联度低、产量低,而且不易制备具有多孔结构的功能性微球。近几年利用微工程乳化技术制备微球的报道越来越多,包括微孔膜/微通道乳化法和微流控技术。这类方法制备的聚苯乙烯-二乙烯苯微球单分散性良好,粒径、孔径等重现性好,为制备多孔聚合物微球开辟了新的方向。 与此同时很多研究者致力于功能性多孔聚苯乙烯-二乙烯苯微球的开发,通过在微球上引入各种功能基团改善微球的疏水性、溶解性和生物亲和性等,制得的不同特性的微球可应用于高效色谱填料、催化剂载体、生物医学、吸附剂等领域。 本文首次详尽地分析和综述了微米级多孔聚苯乙烯-二乙烯苯微球的制备方法和改性方法,讨论了影响微球孔径及孔分布的重要因素,并总结了该类微球近几年的应用研究状况,最后对多孔聚苯乙烯-二乙烯苯微球的发展前景进行了展望。 |
| 英文摘要: |
| As a new type of functional material, microporous polymer microspheres have provoked worldwide research inte-rest. They have particle size ranging from 1 μm to 100 μm, and internal permanent pores from a few angstrom up to several thousands of angstrom in their drying state. Due to their characteristics such as good sphericity, large specific surface area, low density, strong adsorptivity, high mechanical strength and compatibility to various solvents with different polarity, microporous polymer particles have displayed extensive application potential in the fields of the biomedicine, analytical chemistry, environmental protection, catalyst supports and electronic products, etc. Among them, microporous poly(styrene-divinylbenzene) microspheres inherit the ge-neral characteristics of porous polymer microspheres, and moreover, acquire the advantages of favorable physical, chemical and thermal stability, lower production cost and wide industrial applications, as well as high surface reactivity. Thereby microporous poly(styrene-divinylbenzene) microspheres have become the most widely used porous polymer particles at present. Owing to their attractive market prospect, the preparation and functionalization of microporous poly(styrene-divinylbenzene) microspheres have become the research focuses and obtained great success. Over the past decades, various methodologies have been developed and applied to the manufacture of microporous poly(styrene-divinylbenzene) microspheres. Suspension polymerization is the traditional and simple method to prepare poly(styrene-divinylbenzene) microspheres but results in broad particle size distribution. Seed swelling method has advantages on preparing monodispersed poly(styrene-divinylbenzene) microspheres with large size and functional groups. Besides, we can also use precipitation polymerization to obtain monodispersed polymer microspheres, though poor crosslinking density and low yield as well as difficulty to gain porous and functionalized product make this method less promising. Preparing poly(styrene-divinylbenzene) microspheres with microengineering emulsification techniques, including membrane/microchannel emulsification and microfluidics, will alleviate to get controllable size distribution and favorable reproducibility of particle size/pore size distribution. Hence microengineering emulsification opens a new path for the preparation of porous polymer particles. On the other side, noticeable efforts have also been made to introduce different functional groups onto the surface of porous poly(styrene-divinylbenzene) microspheres to impart hydrophilicity, solubility and biological affinity, which enable more diversified use, e.g. chromatographic packing, catalyst supports, biomedical materials and adsorbents. This article pioneers the summary over preparation and functionalization methods, important factors influencing pore size and distribution, with respect to microporous poly(styrene-divinylbenzene) microspheres. It also sketches out the appliance situation in recent years, and makes prospective discussion on the future development. |
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