Research progress in chemical preparation of polymer/inorganic nanoparticle composite microspheres
-
摘要: 聚合物/无机纳米粒子复合微球,具有良好的可设计性、流动性、热稳定性、功能基表面特性等优良的综合性能。聚合物/无机纳米粒子复合微球的形貌、粒径及分布、表面结构等可根据制备方法发生显著变化,从而影响其理化性能。本文综述了乳液聚合法、悬浮聚合法、分散聚合法、两步复合法、自组装法、物理诱导和模板辅助法等化学方法在制备聚合物/无机纳米粒子复合微球方面的研究进展,对其中涉及的多层、核-壳、功能化复合微球的制备方法也做了一定总结。最后,提出了当前在化学制备聚合物/无机纳米粒子复合微球时仍面临的问题,并进行了展望。Abstract: Polymer/inorganic nanoparticle composite microspheres have excellent comprehensive properties such as good designability, fluidity, thermal stability and functional base surface characteristics. The morphology, particle size, distribution and surface structure of polymer/inorganic nanoparticle composite microspheres can be significantly changed according to the preparation method, which can affect their physical and chemical properties. This article reviews the research progress of emulsion polymerization, suspension polymerization, dispersion polymerization, two-step compounding, self-assembly, physical induction and template-assisted methods in preparing polymer/inorganic nanoparticle composite microspheres. The preparation methods of multi-layer, core-shell and functionalized composite microspheres have also been summarized. Finally, the current problems in the chemical preparation of polymer/inorganic nanoparticle composite microspheres are proposed and prospected.
-
Key words:
- inorganic nanoparticle /
- polymer /
- composite microspheres /
- chemical preparation /
- research progress
-
图 1 SiO2@聚苯乙烯(PS)复合微球形成过程示意图 (a)[26]、乳液聚合法制备SiO2@PS复合微球的示意图 (b)[27]、乳液聚合法制备核-壳型Fe3O4@聚乙炔(PA)复合微球的示意图 (c)[29]和乳液聚合法封装Fe3O4磁性纳米粒子的示意图 (d)[32]
Figure 1. Schematic diagram of the formation process of SiO2@Polystyrene (PS) microspheres (a)[26], schematic diagram of preparing SiO2@PS composite microspheres by emulsion polymerization (b)[27], schematic diagram of preparing core-shell Fe3O4@polyacetylene (PA) composite microspheres by emulsion polymerization (c)[29] and schematic diagram of Fe3O4 magnetic nanoparticles encapsulated by emulsion polymerization (d)[32]
Vi-D4—Tetramethyltetraethylene cyclotetrasiloxane; St—Styrene; NPs—Nanoparticles; OPNTU—O-(proparynyl)-N-(triethoxylsilyl) methyl carbamate
图 2 聚甲基丙烯酸甲酯(PMMA)/CaCO3复合微球的SEM图像 (a)[36]、PMMA/CaCO3复合微球的TEM图像 ((b)~(c))[36-37]和PMMA/CaCO3复合微球形成过程示意图 (d)[36]
Figure 2. SEM image of PMMA/CaCO3 composite microspheres (a)[36], TEM images of PMMA/CaCO3 composite microspheres ((b)-(c))[36-37] and scheme illustration of the formation process of PMMA/CaCO3 composite microspheres (d)[36]
图 3 聚(甲基丙烯酸硬脂酯-丙烯酸丁酯)共聚物(PSB)-SiO2复合微球的SEM和TEM图像 ((a)~(b))、PSB-SiO2复合微球的截面图 ((c)~(d)) 和PSB-SiO2复合微球的元素分布图 ((e)~(h))[52]
Figure 3. SEM and TEM images of poly(stearate methacrylate-butyl acrylate) copolymer (PSB)-SiO2 composite microspheres ((a)-(b)), cross section of PSB-SiO2 composite microspheres ((c)-(d)) and element mapping images of PSB-SiO2 composite microspheres ((e)-(h))[52]
图 4 PMMA/TiO2复合微球和纯TiO2悬浮液的稳定性曲线 (a)[59]、SiO2@ PMMA核-壳型复合微球的TEM图像 (b)[61]、石墨烯(GO)@甲基丙烯酸羟乙酯(PHEMA)复合微球的6次循环效率 (c)[62]和核-壳型聚丙烯酸(PAA)/PS/SiO2多层杂化微球的TEM图像 (d)[67]
Figure 4. Sedimentation stability measurement of both PMMA/TiO2 and pristine TiO2 suspensions as a function of time (a)[59], TEM image of PMMA/SiO2 core-shell composite microspheres (b)[61], Efficiency of the graphene (GO)@hydroxyethyl methacrylate (PHEMA) composite after six cycles (c)[62] and TEM image of core-shell SiO2@polyacrylic acid (PAA)@PS multilayer hybrid microspheres (d)[67]
图 5 聚苯胺(PANI)-还原氧化石墨烯(RGO)复合空心微球的制备过程示意图 (a)[79]、PANI-RGO复合空心微球的SEM图像 (b) [79]、PANI-RGO复合空心微球和PANI-RGO复合膜在电流密度为0.5 A/g下的循环性能 (c)[79]和PS@RGO核-壳微球的TEM图像 (d)[81]
Figure 5. Illustration of the fabrication procedure of the polyaniline (PANI)-reduced graphene oxide (RGO) hollow spheres (a)[79], SEM micrograph of PANI-RGO hollow spheres (b)[79], cycling stability of PANI-RGO hollow spheres and PANI-RGO film at a current density of 0.5 A/g (c)[79] and TEM image of the PS@RGO core-shell microspheres (d)[81]
THF—Tetrahydrofuran; HS—Hollow sphere; LBL—Layer-by-layer
-
[1] LIU Y B, LIU J, TIAN Y, et al. Robust organic-inorganic composite films with multifunctional properties of superhydrophobicity, self-healing, and drag reduction[J]. Industrial & Engineering Chemistry Research,2019,58(11):4468-4478. [2] VLASENKO N V, KOCHKIN Y N, SEREBRII T G, et al. Organic-inorganic composites based on gel-type sulfonic resin KU-2-8 and zirconia: Acid and catalytic properties in the etherification reaction of iso-butylene with ethanol[J]. Industrial & Engineering Chemistry Research,2018,57(32):10859-10865. [3] MA Y J, CHEN L, YE Y P, et al. Preparation and tribological behaviors of a novel organic-inorganic hybrid resin bonded solid lubricating coating cured by ultraviolet radiation[J]. Progress in Organic Coatings,2019,127:348-358. doi: 10.1016/j.porgcoat.2018.11.032 [4] GAO Y S, TEOH T W, WANG Q, et al. Electrospun organic–inorganic nanohybrids as sustained release drug delivery systems[J]. Journal of Materials Chemistry B,2017,5(46):9165-9174. doi: 10.1039/C7TB01825H [5] STRIANI R, CORCIONE C E, MUIA G D, et al. Durability of a sunlight-curable organic–inorganic hybrid protective coating for porous stones in natural and artificial weathering conditions[J]. Progress in Organic Coatings,2016,101:1-14. doi: 10.1016/j.porgcoat.2016.07.018 [6] YING G G, GUO S Y, CHEN L P, et al. A novel alveolate-structured organic-inorganic hybrid with high activity for photocatalytic hydrogen evolution[J]. International Journal of Hydrogen Energy,2020,45(24):13202-13210. doi: 10.1016/j.ijhydene.2020.03.060 [7] 赵晓青. 核壳结构有机/无机复合微球的制备与应用进展[J]. 云南化工, 2020, 47(10):15-16.ZHAO X Q. Preparation and application of organic/inorganic composite microspheres with core-shell structure[J]. Yunnan Chemical Technology,2020,47(10):15-16(in Chinese). [8] HOSSEINI M G, ABOUTALEBI K. Improving the anticorro-sive performance of epoxy coatings by embedding various percentages of unmodified and imidazole modified CeO2 nanoparticles[J]. Progress in Organic Coatings: An International Review Journal,2018,12-2:56-63. [9] LI J, MA J, JIANG T, et al. Combined membrane emulsification with biomemetic mineralization: Designing and constructing novel organic-inorganic hybrid microspheres for enzyme immobilization[J]. Composites Science and Technology,2017,141:56-64. doi: 10.1016/j.compscitech.2017.01.008 [10] WU G, GUO S, YIN Y, et al. Hollow microspheres of SiO2/PMMA nanocomposites: Preparation and their application in light diffusing films[J]. Journal of Inorganic and Organometallic Polymers and Materials,2018,28(6):2701-2713. doi: 10.1007/s10904-018-0905-9 [11] ZHANG Q T, XU B, YUAN S S, et al. Fabrication and characterization of sesame ball-like CeO2:Y3+/P(St–AA) composite microspheres based on electrostatic interaction[J]. Materials Letters,2014,121:109-112. doi: 10.1016/j.matlet.2014.01.082 [12] WEERAKKODY C, GUILD C, ACHOLA L A, et al. Effects of microwave and ultrasound exposure to microsphere particles made out of different classes of inorganic and organic materials[J]. Journal of Industrial and Engineering Chemistry,2018,65:26-30. doi: 10.1016/j.jiec.2018.04.032 [13] LUO J, CHEN Y X, ZHENG Y, et al. Hollow graphene-polyaniline hybrid spheres using sulfonated graphene as Pickering stabilizer for high performance supercapacitors[J]. Electrochimica Acta,2018,272:221-232. doi: 10.1016/j.electacta.2018.04.011 [14] ZHOU M J, ZHOU S Z, PANG X C, et al. Preparation of superparamagnetic gamma-Fe2O3@LS@PS copmposite latex particles through pickering miniemulsion polymerization[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2020,585:124040. doi: 10.1016/j.colsurfa.2019.124040 [15] SHI X Z, DUAN J P, LU J J, et al. A novel fabrication method of network-like polyimide/silica composite microspheres with a high SiO2 content[J]. Materials Letters,2014,128(128):5-8. [16] WANG Z, LI S C, WU Z J. The fabrication and properties of a graphite nanosheet/polystyrene composite based on graphite nanosheets treated with supercritical water[J]. Composites Science & Technology,2015,112:50-57. [17] KHARISMADEWI D, HALDORAI Y, NGUYEN V H, et al. Synthesis of graphene oxide-poly(2-hydroxyethyl methacrylate) composite by dispersion polymerization in supercritical CO2: Adsorption behavior for the removal of organic dye[J]. Composite Interfaces,2016,23(7):1-21. [18] YE W Q, ZAHNG L, FENG G W, et al. Preparation of calcium carbonate@methyl methacrylate nanoparticles by seeded-dispersion polymerization for high performance polyvinyl chloride nanocomposites[J]. Industrial & Engineerig Chemistry Research,2015,54(30):7459-7464. [19] TRITSCHLER U, CÖLFEN H. Self-assembled hierarchically structured organic-inorganic composite systems[J]. Bioinspiration & Biomimetics,2016,11(3):35002. [20] WANG Z D, YANG M M, CHENG Y H, et al. Dielectric properties and thermal conductivity of epoxy composites using quantum-sized silver decorated core/shell structured alumina/polydopamine[J]. Composites Part A: Applied Science & Manufacturing,2018,118:302-311. [21] ZHANG M M, NGO T H, RABIAH N I, et al. Core-shell and asymmetric polystyrene-gold composite particles via one-step pickering emulsion polymerization[J]. Langmuir,2015,30(1):75-82. [22] YANG D X, WANG X X, WANG N, et al. In-situ growth of hierarchical layered double hydroxide on polydopamine-encapsulated hollow Fe3O4 microspheres for efficient removal and recovery of U(VI)[J]. Journal of Cleaner Production,2018,172(2):2033-2044. [23] MA Y C, YANG D Y, JIANG Q, et al. TiN-based organic-inorganic composite films with dual functions of solar control and low-emission for energy-saving coatings[J]. Materials Research Express,2020,7(6):65504. doi: 10.1088/2053-1591/ab96fd [24] 高山, 陕绍云, 李丹, 等. 聚苯胺/银纳米复合材料的形貌对抗菌性能的影响[J]. 高分子材料科学与工程, 2012, 28(2):60-63.GAO S, SHAN S Y, LI D, et al. Effect of morphologies of polyaniline/silver nanocomposite on its antibacterial properties[J]. Polymer Materials Science and Engineering,2012,28(2):60-63(in Chinese). [25] ATHAWALE V D, KULKARNI M A. Synthesis and perfor-mance evaluation of polyurethane/silica hybrid resins[J]. Pigment & Resin Technology,2011,40(1):49-57. [26] 王莉. SiO2/高分子核壳材料及交联聚合物的制备[D]. 长春: 吉林大学, 2006.WANG L. Synthesis of SiO2/polymer composite materials and cross-linked polymer[D]. Changchun: Jilin University, 2006(in Chinese). [27] ZHANG K, WU W, MENG H, et al. Pickering emulsion polymerization: Preparation of polystyrene/nano-SiO2 compo-site microspheres with core-shell structure[J]. Powder Technology,2009,190(3):393-400. doi: 10.1016/j.powtec.2008.08.022 [28] CAI L F, WANG C L, LIN W, et al. Synthesis and adsorption properties of composite microsphere with dual-magnetic responses[J]. Acta Scientiarum Naturalium Universitatis Sunyatseni,2016,55(4):75. [29] CHEN H Y, ZHOU J Y, DENG J P. Helical polymer/Fe3O4 NPs constructing optically active, magnetic core/shell microspheres: Preparation by emulsion polymerization and recycling application in enantioselective crystallization[J]. Polymer Chemistry,2015,7(1):125-134. [30] YU L H, HAO G Z, GU J J, et al. Fe3O4/PS magnetic nanoparticles: Synthesis, characterization and their application as sorbents of oil from waste water[J]. Journal of Magnetism and Magnetic Materials,2015,394:14-21. doi: 10.1016/j.jmmm.2015.06.045 [31] 黄增芳, 瞿晓岳, 马军现. 乳液聚合制备SiO2/PMMA-DMEMA亚微米复合微球及表征[J]. 高分子材料科学与工程, 2014, 30(1):127-130.HUANG Z F, QU X Y, MA J X. Characterization of the submicron SiO2/PMMA-DMEMA composite microspheres prepared by the emulsion polymerization[J]. Polymer Materials Science and Engineering,2014,30(1):127-130(in Chinese). [32] DU H, ZHANG P, LIU F Q, et al. Trilayer composite poly(styrene/butyla-crylate/acrylic acid) terpolymer microspheres with Fe2O3 middle layer: Synthesis and characterization[J]. Polymer International,1997,43(3):274-280. doi: 10.1002/(SICI)1097-0126(199707)43:3<274::AID-PI773>3.0.CO;2-D [33] LI Y X, WANG Z Q, GU H, et al. A facile strategy for synthesis of multilayer and conductive organo-silica/polystyrene/polyaniline composite particles[J]. Journal of Colloid and Interface Science,2011,355(2):269-273. doi: 10.1016/j.jcis.2010.12.061 [34] LIU B, BAI C, ZHAO D, et al. Novel ferroferric oxide/polystyrene/silver core-shell magnetic nanocomposite microspheres as regenerable substrates for surface-enhanced Raman scattering[J]. Applied Surface Science,2015,364:628-635. [35] KUMAR M J K, KALATHI J T. Interface dominated dielectric response of PS-Fe3O4 patchy microspheres[J]. Langmuir,2019,35(43):13923-13933. [36] MA X K, ZHOU B, SHENG Y, et al. Preparation of calcium carbonate/poly(methyl methacrylate) composite microspheres by soapless emulsion polymerization[J]. Journal of Applied Polymer Science,2007,105(5):2925-2929. doi: 10.1002/app.26486 [37] MA X K, ZHOU B, DENG Y H, et al. Study on CaCO3/PMMA nanocomposite microspheres by soapless emulsion polymerization[J]. Colloids & Surfaces A Physicochemical & Engineering Aspects,2008,312(2-3):190-194. [38] DUAN Y F, FU Z X, LI Y, et al. Preparation and characterization of nano composite microspheres of polystyrene and Fe3O4 by emulsifier-free emulsion polymerization[J]. Advanced Materials Research,2013,804:123-128. doi: 10.4028/www.scientific.net/AMR.804.123 [39] LI J Q S, WANG H, WANG Y Q. Preparation of silica/polymer hybrid nanoparticles via a semi-continuous soup-free emulsion polymerization[J]. Advanced Materials Research,2015,1120-1121:233-242. doi: 10.4028/www.scientific.net/AMR.1120-1121.233 [40] JIANG X L, GUO W W, YOU F, et al. Enhancing the dielectric properties of polymethyl methacrylate by using low loading graphene encapsulated styrene-butyl acrylate copolymer microspheres[J]. Synthetic Metals,2020,259:116229. doi: 10.1016/j.synthmet.2019.116229 [41] ERDEM B, SUDOL E D, DIMONIE V L, et al. Encapsulation of inorganic particles via miniemulsion polymerization. I. Dispersion of titanium dioxide particles in organic media using OLOA 370 as stabilizer[J]. Journal of Polymer Science Part A Polymer Chemistry,2000,38(24):4419-4430. doi: 10.1002/1099-0518(20001215)38:24<4419::AID-POLA110>3.0.CO;2-X [42] AL-GHAMDI G H, SUDOL E D, DIMONIE V L, et al. Encapsulation of titanium dioxide in styrene/nbutyl acrylate copolymer by miniemulsion polymerization[J]. Journal of Applied Polymer Science,2006,101(5):3479-3486. doi: 10.1002/app.24478 [43] LUO Y D, DAI C A, CHIU W W. Nucleation mechanism and morphology of polystyrene/Fe3O4 latex particles via miniemulsion polymerization using AIBN as initiator[J]. Journal of Applied Polymer Science,2009,112(2):975-984. doi: 10.1002/app.29481 [44] ZHOU J, ZHANG S W, QIAO X G, et al. Synthesis of SiO2/poly(styrene-co-butyl acrylate) nanocomposite microspheres via miniemulsion polymerization[J]. Journal of Polymer Science Part A Polymer Chemistry,2006,44(10):3202-3209. doi: 10.1002/pola.21434 [45] WU Y F, ZHANG Y, XU J X, et al. One-step preparation of PS/TiO2 nano-composite particles via miniemulsion polymerization[J]. Journal of Colloid & Interface Science,2010,343(1):18-24. [46] SCHOTH A, WAGNER C, HECHT L L, et al. Structure control in PMMA/silica hybrid nanoparticles by surface functionalization[J]. Colloid & Polymer Science,2014,292(10):2427-2437. [47] ZHOU J, CHEN M, QIAO X G, et al. Facile preparation method of SiO2/PS/TiO2 multilayer core-shell hybrid microspheres[J]. Langmuir,2006,22(24):10175-10179. doi: 10.1021/la062220h [48] LI X P, LU M Y, AI S L, et al. Morphology and kinetic mechanism of facile one-step preparing TiO2/polyacrylate/TiO2 multilayer core-shell hybrid emulsion via miniemulsion polymerization[J]. Journal of Adhesion Science & Technology,2015,29(19):2049-2064. [49] 谢琳. 有机-无机杂化纳米复合空球的制备及性能研究[D]. 上海: 复旦大学, 2010.XIE L. Preparation of organic-inorganic hybrid nanocomposite hollow spheres and their properties[D]. Shanghai: Fudan University, 2010(in Chinese). [50] 孔丝纺, 文秀芳, 皮丕辉, 等. 磁性多孔γ-Fe2O3/P(St-DVB-MAA)聚合物微球的制备及其表征[J]. 高分子学报, 2008, 8(2):168-173. doi: 10.3321/j.issn:1000-3304.2008.02.012KONG S F, WEN X F, PI P H, et al. Preparation and characterizationof magneticporous γ-Fe2O3 P(St-DVB-MAA) polymer microspheres preparation and characterization of magnetic porous γ-Fe2O3/P(St-DVB-MAAA) polymer microspheres[J]. Acta Polymerrica Sinica,2008,8(2):168-173(in Chinese). doi: 10.3321/j.issn:1000-3304.2008.02.012 [51] ZHOU S, XU J L, YONG J S, et al. Preparation of monodisperse functional polystyrene/silica microsphere compo-site via suspension polymerization method[J]. Applied Mechanics & Materials,2014,470:66-69. [52] DUAN Y J, BIAN F L, HUANG H J. A novel composite microsphere as a highly efficient absorbent for oils and organic solvents[J]. Polymers for Advanced Technologies,2016,27(11):1494-1500. doi: 10.1002/pat.3819 [53] MA R, TANG W, HU P, et al. Fabrication of low-density heat-resistance polystyrene/carbon black composite microspheres used as hydraulic fracturing proppant[J]. Materials Express,2019,9(2):150-158. doi: 10.1166/mex.2019.1478 [54] DAO T D, ERDENEDELGER G, JEONG H M. Water-dipersible graphene designed as a Pickering stabilizer for the suspension polymerization of poly(methyl methacrylate)/graphene core-shell microsphere exhibiting ultra-low percolation threshold of electrical conductivity[J]. Polymer,2014,55(18):4709-4719. doi: 10.1016/j.polymer.2014.07.038 [55] DUAN L L, CHEN M, ZHOU S X, et al. Synthesis and characterization of poly(N-isopropylacrylamide)/silica compo-site microspheres via inverse Pickering suspension polymerization[J]. Langmuir,2009,25(6):3467-3472. [56] ZHOU H O, SHI T J, ZHOU X. Poly(vinyl alcohol)/SiO2 composite microsphere based on Pickering emulsion and its application in controlled drug release[J]. Journal of Biomaterials Science, Polymer Edition,2014,25(7):641-656. doi: 10.1080/09205063.2014.890919 [57] JAMALI A, MOGHBELI M R, AMELI F, et al. Synthesis and characterization of pH-sensitive Poly(acrylamide-co-methylenebisacrylamide-co-acrylic acid) hydrogel microspheres containing silica nanoparticles: Application in enhanced oil recovery processes[J]. Journal of Applied Polymer Science,2020,137(12):48491. doi: 10.1002/app.48491 [58] LIN Y, KE Y C, YU C C, et al. Encapsulation of anion-cation organo-montmorillonite in terpolymer microsphere: Structure, morphology, and propertyes[J]. Journal of Polymer Engineering,2020,40(4):321-332. doi: 10.1515/polyeng-2019-0291 [59] PARK B J, SUNG J H, KIM K S, et al. Preparation and characterization of poly(methyl methacrylate) coated TiO2 nanoparticles[J]. Journal of Macromolecular Science Part B-Physics,2006,45(1):53-60. doi: 10.1080/00222340500407855 [60] 曹康丽, 史铁钧, 曹金燕, 等. 分散聚合法制备SiO2/PAM核壳复合微球[J]. 高分子材料科学与工程, 2008, 24(4):42-45. doi: 10.3321/j.issn:1000-7555.2008.04.010CAO K L, SHI T J, CAO J Y, et al. Synthesis of SiO2/PAM core/shell composite microspheres by dispersion polymerization[J]. Polymer Materials Science and Engineering,2008,24(4):42-45(in Chinese). doi: 10.3321/j.issn:1000-7555.2008.04.010 [61] 魏铭, 佘新光, 刘晓芳, 等. 分散聚合法制备PMMA/SiO2核壳型杂化微球[J]. 武汉理工大学学报, 2010, 32(10):29-32. doi: 10.3963/j.issn.1671-4431.2010.10.007WEI M, SHE X G, LIU X F, et al. Synthesis of SiO2/PMMA core shell hybrid microspheres by dispersion polymerization[J]. Journal of Wuhan University of Technology,2010,32(10):29-32(in Chinese). doi: 10.3963/j.issn.1671-4431.2010.10.007 [62] KHARISMADEWI D, HALDORAI Y, NGUYEN V H, et al. Synthesis of graphene oxide-poly(2-hydroxyethyl methacrylate) composite by dispersion polymerization in supercritical CO2: Adsorption behavior for the removal of organic dye[J]. Composite Interfaces,2016,23(7):719-739. doi: 10.1080/09276440.2016.1169707 [63] ZHANG J H, DING X B, PENG Y X, et al. Magnetic polymer microsphere with photoconductivity: Preparation and characterization of iron(III) phthalocyanine covalently bonded on to polystyrene microsphere surface[J]. Polymer International,2002,51(7):617-621. doi: 10.1002/pi.929 [64] FAN L H, LUO Y L, CHEN Y S, et al. Preparation and characterization of Fe3O4 magnetic composite microspheres covered by a P(MAH-co-MAA) copolymer[J]. Journal of Nanoparticle Research,2009,11(2):449-458. doi: 10.1007/s11051-008-9556-z [65] 严海晨, 李延报. 分散聚合原位制备聚苯乙烯/氧化石墨烯复合微球[J]. 南京工业大学学报(自然科学版), 2019, 41(2):135-140.YAN H C, LI Y B. Situ preparation of polystyrene/graphene composite microspheres by the dispersion polymerization[J]. Journal of Nanjing Tech University (Natural Science Edition),2019,41(2):135-140(in Chinese). [66] HWANG D R, HONG J H, HONG C K, et al. Synthesis of positively charged silica-coated polystyrene microspheres via dispersion polymerization initiated with amphoteric initiator[J]. Journal of Dispersion Science & Technology,2010,31(2):155-161. [67] WANG H L, SHI T J, ZHAI L F. Preparation of core-shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres[J]. Journal of Applied Polymer Science,2006,102(2):1729-1733. doi: 10.1002/app.24354 [68] TISSOT I, NOVAT C, LEFEBVRE F, et al. Hybrid latex particles coated with silica[J]. Macromolecules,2001,34(17):5737-5739. doi: 10.1021/ma010278r [69] KIM O H, HWANG M J, RYU D W, et al. Synthesis and characterization of monodispersed core-shell/polystyrene-silica composite nanospheres as artificial dusts[J]. Journal of Nanoscience and Nanotechnology,2013,13(6):4271-4274. doi: 10.1166/jnn.2013.7004 [70] ANGELOPOULOU A, EFTHIMIADOUA E K, BOUKOSA N, et al. A new approach for the one-step synthesis of bioactive PS vs. PMMA silica hybrid microspheres as potential drug delivery systems[J]. Colloids and Surfaces B: Biointerfaces,2014,117:322-329. doi: 10.1016/j.colsurfb.2014.02.047 [71] KARABACAKA R B, ERDEMA M, YURDAKALB S, et al. Facile two-step preparation of polystyrene/anatase TiO2 core/shell colloidal particles and their potential use as an oxidation photocatalyst[J]. Materials Chemistry and Physics,2014,144(3):498-504. doi: 10.1016/j.matchemphys.2014.01.026 [72] SUN X F, SUN B, GONG Q H, et al. Double-shell structural polyaniline-derived TiO2 hollow spheres for enhanced photocatalytic activity[J]. Transition Metal Chemistry,2019,44(6):555-564. doi: 10.1007/s11243-019-00312-8 [73] CARUSO F, CARUSO R A, MÖHWALD H. Nanoengineering of inorganic and hybrid hollow spheres by colld-idal templating[J]. Science,1998,282(5391):1111-1114. doi: 10.1126/science.282.5391.1111 [74] GUO F, ZHU Y H, YANG X L, et al. Electrostatic layer-by-layer self-assembly of PAMAM–CdS nanocomposites on MF microspheres[J]. Materials Chemistry & Physics,2007,105(2-3):315-319. [75] JIANG S D, TANG G, CHEN J M, et al. Biobased polyelectrolyte multilayer-coated hollow mesoporous silica as a green flame retardant for epoxy resin[J]. Journal of Hazardous Materials,2018,342:689-697. doi: 10.1016/j.jhazmat.2017.09.001 [76] ZHAO Q C. Self-assembly of CdSe quantum dots and colloidal titanium dioxide on copolymer microspheres (PS) for CdSe/PS and TiO2/CdSe/PS submicrospheres with yolk-shell structure[J]. Applied Surface Science,2015,344:107-111. doi: 10.1016/j.apsusc.2015.03.062 [77] 宋月英, 韩丁, 关晓林, 等. 自组装法制备磺化聚苯乙烯@Fe3O4磁性复合颗粒及其磁性能[J]. 复合材料学报, 2020, 37(6):1364-1369.SONG Y Y, HAN D, GUAN X L, et al. Preparation and magnetic propertyes of sulfonated polystyrene @Fe3O4 magnetic composite particles by self-assembly method[J]. Acta Materiae Compositae Sinica,2020,37(6):1364-1369(in Chinese). [78] ZHU L F, WANG H, SHEN X S, et al. Developing mutually encapsulating materials for versatile syntheses of multilayer metal-silica-polymer hybrid nanostructures[J]. Small,2012,8(12):1857-1862. doi: 10.1002/smll.201102670 [79] LUO J, MA Q, GU H H, et al. Three-dimensional graphene-polyaniline hybrid hollow spheres by layer-by-layer assembly for application in supercapacitor[J]. Electrochimica Acta,2015,184:184-192. [80] YANG J T, YAN X H, WU M J, et al. Self-assembly between graphene s-heets and cationic poly(methyl methacrylate) (PMMA) particles: Preparation and characterization of PMMA/graphene composites[J]. Journal of Nanoparticle Research,2012,14(1):717. doi: 10.1007/s11051-011-0717-0 [81] LI Y, XU Y, ZHOU T, et al. A method to construct perfect 3D polymer/graphene oxide core–shell microspheres via electrostatic self-assembly[J]. RSC Advances,2015,5(41):32469-32478. doi: 10.1039/C5RA01984B [82] LIU X B, WEN N, WANG X L, et al. A high-performance hierarchical graphene@polyaniline@graphene sandwich containing hollow structures for supercapacitor electrodes[J]. ACS Sustainable Chemistry & Engineering,2015,3(3):475-482. [83] ZHANG S Q, ZHU Y H, YANG X L, et al. Fabrication of core–shell latex spheres with CdS/polyelectrolyte composite multilayers[J]. Colloids & Surfaces A,2005,264(1-3):215-218. [84] BAI W B, YAO R J, TIAN X, et al. Sunlight highly photoactive TiO2@poly-p-phenylene composite microspheres for malachite green degradation[J]. Journal of the Taiwan Institute of Chemical Engineers,2018,87:112-116. doi: 10.1016/j.jtice.2018.03.018 [85] YIN J L, QIAN X F, YIN J, et al. Preparation of ZnS/PS microspheres and ZnS hollow shells[J]. Materials Letters,2003,57(24-25):3859-3863. doi: 10.1016/S0167-577X(03)00217-9 [86] BARKADE S S, PINJARI D V, SINGH A K, et al. Ultrasound assisted miniemulsion polymerization for preparation of polypyrrole−zinc oxide (PPy/ZnO) functional latex for liquefied petroleum gas sensing[J]. Industrial & Engineering Chemistry Research,2013,52(23):7704-7712. [87] PRADID J, KEAWWATANA W, BOONYANG U, et al. Biological properties and enzymatic degradation studies of clindamycin loaded PLA/HAp microspheres prepared from crocodile bones[J]. Polymer Bulletin,2017,74(12):5181-5194. doi: 10.1007/s00289-017-2006-2 [88] PANIGRAHI R, SRIVASTAVA S K. Tollen’s reagent assisted synthesis of hollow polyaniline microsphere/Ag nanocomposite and its applications in sugar sensing and electromagnetic shielding[J]. Materials Research Bulletin,2015,64:33-41. doi: 10.1016/j.materresbull.2014.12.035 [89] ZHANG S P, SONG X Z, LIU S H, et al. Template-assisted synthesized MoS2/polyaniline hollow microsphere electrode for high performance supercarpacitors[J]. Electrochimica Acta,2019,312:1-10. doi: 10.1016/j.electacta.2019.04.177