分散聚合两步法制备壳交联聚合物微球及自模板制备空心球

张友稳;刘莲英;张芬;杨万泰*

北京化工大学学报(自然科学版) ›› 2010, Vol. 37 ›› Issue (6) : 86-91.

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北京化工大学学报(自然科学版) ›› 2010, Vol. 37 ›› Issue (6) : 86-91.
材料科学与工程

分散聚合两步法制备壳交联聚合物微球及自模板制备空心球

  • 张友稳;刘莲英;张芬;杨万泰*
作者信息 +

Preparation of core-shell and hollow polymer particles by two-stage dispersion polymerization

  • ZHANG YouWen;LIU LianYing;ZHANG Fen;YANG WanTai
Author information +
文章历史 +

摘要

采用分散聚合两步加料法,在单体苯乙烯(St)转化率达80%以上时加入交联剂二乙烯基苯(DVB),以未交联内核自身为模板,制备了PS核-P(St-DVB)壳(壳交联)结构微球。然后使用PS的良溶剂THF将未交联内核溶出后,制得了结构规整的空心聚合物微球。采用扫描电镜(SEM)及透射电镜(TEM)观察了所得核-壳、空心球的形貌,探讨了核-壳聚合物微球制备过程引发剂用量、单体浓度及交联剂用量对最终所得空心球形貌的影响。结果表明:增大引发剂用量,微球内核聚合物的分子量减小,内核容易溶出;增大起始单体浓度,壳层交联剂含量相对减小,所得空心球易破裂,刚度下降;单体浓度过低可使交联层致密,不利于内核聚合物溶出,得到蜂窝状空心球;交联剂用量增加,所得空心球的刚度和壁厚增加。

Abstract

Monodisperse polystyrene (PSt) core-cross-linked poly(styrene-divinylbenzene) (P(St-DVB) shell microspheres have prepared by a two-stage dispersion polymerization in which DVB was charged into the reaction system after St monomer conversion reached as high as 80%. The cross-linking mainly took place at the surface. Subsequently, hollow particles composed of the cross-linked P(St-DVB) were prepared by treating the core-shell microspheres with THF in which the core PSt polymer dissolved and was removed. The morphology of the hollow particles was observed by SEM and TEM. The influence of varying the synthesis parameters was investigated. The results indicated that perfect hollow particles could be readily produced if appropriate concentrations of initiator and monomer were used in the first dispersion polymerization. By increasing the amount of the crosslinker employed in the dispersion polymerization, hollow particles with suitable thickness and rigidity can be fabricated. 

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张友稳;刘莲英;张芬;杨万泰*. 分散聚合两步法制备壳交联聚合物微球及自模板制备空心球[J]. 北京化工大学学报(自然科学版), 2010, 37(6): 86-91
ZHANG YouWen;LIU LianYing;ZHANG Fen;YANG WanTai. Preparation of core-shell and hollow polymer particles by two-stage dispersion polymerization[J]. Journal of Beijing University of Chemical Technology, 2010, 37(6): 86-91

参考文献

1]Dong A G, Wang Y J, Wang D J, et al. Fabrication of hollow zeolite microcapsules with tailored shapes and functionalized interiors[J]. Microp Mesop Mater, 2003, 64: 69-81.
[2]Hotz J, Meier W. Polymer particles by templating of vesicles[J]. Adv Mater, 1998, 10: 1387-1390.
[3]Yin Y, Lu Y, Gates B, et al. Synthesis and characterization of mesoscopic hollow spheres of ceramic materials with functionalized interior surfaces[J]. Chem Mater, 2001, 13: 1146-1148.
[4]Kim J W, Lee K S, Ju H K, et al. Microencapsulation of cholesteryl alkanoate by polymerization-induced phase separation and its association with drugs[J]. J Polym Sci Part A: Polym Chem, 2004, 42: 2202-2213.
[5]Lu L B, Huang K L. Preparation of poly (propylene-co-g-butyrolactone carbonate) and release profiles of drugloaded microcapsules[J]. J Polym Sci: Part A: Polym Chem, 2005, 43: 2468-2475.
[6]张萍, 冯年平, 武培怡. 聚合物空心纳米球及其在药学领域的应用[J]. 药学进展, 2006, 30(8): 350-353.
Zhang P, Feng N P, Wu P Y. Polymeric hollow nano spheres and the application in pharmacy thereof[J]. Progress in Pharmaceutical Sciences, 2006, 30(8): 350-353. (in Chinese)
[7]Okubo M, Konishi Y, Inohara T, et al. Production of hollow polymer particles by suspension polymerizations for ethylene glycol dimethacrylate/toluene droplets dissolving styrene-methyl methacrylate copolymers[J]. Journal of Applied Polymer Science, 2002, 86(5): 1087-1091.
[8]Minami H, Kobayashi H, Okubo M. Preparation of hollow polymer particles with a single hole in the shell by SASEP[J]. Langmuir, 2005, 21: 5655-5658.
[9]Kim B S, Kim J W, Suh K D. Poly(methyl methacrylate) multihollow particles by water in oil in water emulsion polymerization[J]. Applied Polymer Science, 2000, 76: 38-44.
[10]Chang M W, Stride E, Edirisinghe M. A new method for the preparation of monoporous hollow microspheres[J]. Langmuir, 2010, 26: 5115-5121.
[11]郭生伟, 王琪, 赵越. 超声辐照乳液聚合制备聚丙烯酸正丁酯空心微球[J]. 高分子学报, 2009(9): 891-895.
Guo S W, Wang Q, Zhao Y. Pba hollow microspheres prepared through ultrasonically initiated encapsulation emulsion polymerization[J]. Acta Polymerica Sinica, 2009(9): 891-895. (in Chinese)
[12]He T, Chen D R, Jiao X L, et al. Surfactant-assisted solvothermal synthesis of Co3O4 hollow spheres with oriented-aggregation nanostructures and tunable particle size[J]. Langmuir, 2004, 20: 8404-8408.
[13]Li Z Z, Wen L X, Shao L, et al. Fabrication of porous hollow silica nanoparticles and their applications in drug release control[J]. J Controlled Release, 2004, 98: 245-254.
[14]Bourlinos A, Boukos N, Petridis D. Exchange resins in shape fabrication of hollow inorganic and carbonaceous-inorganic composite spheres[J]. Adv Mater, 2002, 14: 21-24.
[15]刘文芳, 郭朝霞, 于建. PS/CaCO3复合纳米粒子及PS纳米空心球的制备研究[J]. 高分子学报, 2009(2): 134-139.
Liu W F, Guo Z X, Yu J. Preparation of PS/CaCO3 composite nanoparticles and PS hollow nanospheres[J]. Acta Polymerica Sinica, 2009(2): 134-139. (in Chinese)
[16]Schmidt H T, Ostafin A E. Liposome directed growth of calcium phosphate nanoshells[J]. Adv Mater, 2002, 14: 532-535.
[17]Wu M, Wang G, Xu H, et al. Hollow spheres based on mesostructured lead titanate with amorphous framework[J]. Langmuir, 2003, 19: 1362-1367.[18]Fowler C E, Khushalani D, Mann S J. Facile synthesis of hollow silica microspheres[J]. Mater Chem, 2001, 11: 1968-1971.
[19]Song J S, Chagal L, Winnik M A. Monodisperse, controlled micron-size dye-labeled polystyrene particles by two-stage dispersion polymerization[J]. Polymer, 2006, 47: 817-825.
[20]Song J S, Chagal L, Winnik M A. Cross-Linked, Monodisperse, MicronSized Polystyrene Particles by Two-Stage Dispersion Polymerization[J]. Macromolecules, 2005, 38: 8300-8307.
[21]Song J S, Chagal L, Winnik M A. Monodisperse micrometer-size carboxylfunctionalized polystyrene particles obtained by two-stage dispersion polymerization[J]. Macromolecules, 2006, 39: 5729-5737.
[22]王占丽, 刘莲英, 邓建平, 等. 分散聚合制备单分散阳离子型聚苯乙烯微球[J]. 北京化工大学学报: 自然科学版, 2007, 34 (1): 39-43.
Wang Z L, Liu L Y, Deng J P, et al. Monodispersed cationic microspheres of polystyrene prepared by dispersion polymerization[J]. Journal of Beijing University of Chemical Technology: Natural Science, 2007, 34 (1): 39-43. (in Chinese)
[23]Zhang F, Cao L, Yang W T. Preparation of monodisperse and anioncharged polystyrene microspheres stabilized with polymerizable sodium styrene sulfonate by dispersion polymerization[J]. Macromol Chem Phys, 2010, 211: 744-751.

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