高等学校化学学报 ›› 2023, Vol. 44 ›› Issue (1): 20220627.doi: 10.7503/cjcu20220627
沈欣怡1,2,张森1,2,王树涛1,2,3,宋永杨1,2()
收稿日期:
2022-09-21
出版日期:
2023-01-10
发布日期:
2022-11-26
基金资助:
SHEN Xinyi1,2, ZHANG Sen1,2, WANG Shutao1,2,3, SONG Yongyang1,2()
Received:
2022-09-21
Online:
2023-01-10
Published:
2022-11-26
Contact:
SONG Yongyang
E-mail:yysong@mail.ipc.ac.cn
Supported by:
摘要:
在过去的20年中, 聚合物中空微球由于其独特的结构和优异的性质受到了广泛的关注. 它们表现出低密度、 高比表面积和高负载力的特性, 在催化、 药物递送及能量存储等领域中展现出巨大的应用前景. 本文综合评述了聚合物中空微球的合成策略, 主要包括模板法、 乳液聚合法、 自组装与及微流控等, 并详细阐述和讨论了这些合成策略的原理、 典型过程以及优缺点. 同时, 还指出了现有合成策略面临的挑战以及聚合物中空微球存在的不足, 并对聚合物中空微球的制备和应用前景进行了展望.
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沈欣怡, 张森, 王树涛, 宋永杨. 聚合物中空微球的合成策略. 高等学校化学学报, 2023, 44(1): 20220627.
SHEN Xinyi, ZHANG Sen, WANG Shutao, SONG Yongyang. Synthesis Strategies for Polymer Hollow Particles. Chem. J. Chinese Universities, 2023, 44(1): 20220627.
Fig.1 Hard template strategy for the synthesis of polymer hollow microparticles(A) Preparation of PMAA microparticles using SiO2 microspheres as hard template. The process includes synthesis of SiO2 microspheres with vinyl groups on the surface, in situ polymerization of MAA on SiO2 microspheres and etching of SiO2 microspheres by HF. (B) Scanning electron microscopy(SEM) image and transmission electron microscope(TEM) image of PMAA hollow particles[24]. (C) TEM image of PMMA hollow microspheres[26].(A, B) Copyright 2008, American Chemical Society; (C) Copyright 2006, Wiley-VCH.
Fig.2 Soft template strategy for the synthesis of polymer hollow particles(A) Oil (o-methoxyaniline) droplets stabilized by molecular surfactants as soft template[30]. (B) Oil droplets stabilized by nanoparticles as soft template[32]. (C) Water droplets stabilized by colloidal particles as soft template[35]. (D) Air bubbles as soft template stabilized by Tween/Span mixture[29].(A) Copyright 2007, American Chemical Society; (B) Copyright 2010, American Chemical Society; (C) Copyright 2002, American Association for the Advancement of Science; (D) Copyright 2005, Wiley-VCH.
Fig.3 Emulsion polymerization strategy for the synthesis of polymer hollow particles(A) Seed polymerization. Seed polymer particles are first swollen by monomers and initiators, and then phase separation occurs upon the polymerization of monomers, resulting in hollow particles with a hole[40]. (B) Interfacial polymerization. Hydrophilic and hydrophobic monomers are confined to the O/W emulsion interface for polymerization[42]. (C) Supramolecular emulsion interfacial polymerization[45]. Supramonomers(UPy-SH)2 are dissolved in oil, and MA-C12 are dissolved in water, respec- tively. (UPy-SH)2 first aggregate at the interface of emulsion to form nanospheres, and stable nanospheres can be fabricated through polymerization at emulsion interface.(A) Copyright 2008, American Chemical Society; (B) Copyright 2005, American Chemical Society; (C) Copyright 2019, American Chemical Society.
Fig.4 Self⁃assembly strategy for the synthesis of polymer hollow particles(A) Nanofiber hollow spheres are fabricated by self-assembly of star-shaped PLLA[48]. (B) Diblock copolymer that can be used for the preparation of polymer hollow microspheres via self-assembly[50]. (C) Triblock copolymer that can be used for the preparation of polymer hollow microspheres via self-assembly[51].(A) Copyright 2011, Springer Nature; (B) Copyright 2003, American Chemlical Society; (C) Copyright 2000, the Royal Society of Chemistry.
Fig.5 Microfluidic strategy for the synthesis of polymer hollow microspheres(A) A typical capillary microfluidic device for the preparation of G/O/W emulsion[62]. (B) Phase separation occurs in the polymer-solvent droplet prepared by microfluidic strategy, obtaining hollow microspheres[64]. (C) SEM images and scheme of hollow polymer particles with interconnected shell[66].(A) Copyright 2012, the Royal Society of Chemistry; (B) Copyright 2015, American Chemical Society; (C) Copyright 2017, American Chemical Society.
Fig.6 Other strategies for the synthesis of hollow polymer particles(A) Freezing strategy. This strategy includes swelling of the polymer(PS) microparticles by solvent(toluene), freezing, and evaporation of the solvent by warming up[67]. (B) Direct synthesis strategy[68]. Allyls(disk-shaped monomers) are linked by dithiol, forming 2D dimer or trimer oligomeric patches, then loosely cross-linked polymer nanocapsules, and finally extensively cross-linked polymer nanocapsules. (C) Coordination polymer one-pot solvothermal reaction strategy[74]. Initial solid spheres are composed of smaller polymer crystallites. Mass transfer from interior to exterior by a dissolution-outmigration process, constructing coordination polymer hollow particles with interior cavity and surface micropores. Formation process and TEM images of the initial solid microspheres and resultant hollow coordination polymer microspheres.(A) Copyright 2005, Springer Nature; (B) Copyright 2007, Wiley-VCH; (C) Copyright 2010, Wiley-VCH.
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