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Preparation and Charecterization of Charged Hollow Double-layer Polyelectrolyte Microspheres
- Acta Polymerica Sinica Vol. 0, Issue 7, Pages: 900-908(2018)
- 作者机构：
1.功能高分子材料教育部重点实验室 南开大学高分子化学研究所 天津 300071
2.海南大学材料与化工学院 海口 570228
- 作者简介：
- 基金信息：
DOI：10.11777/j.issn1000-3304.2018.18028
CLC：Published：2018-7，
Received：24 January 2018，
Revised：28 March 2018，
扫 描 看 全 文
Dan Wang, Li-jie Luo, Gao-long Wu, Bin Liu, Yong-jun Chen, Xin-lin Yang. Preparation and Charecterization of Charged Hollow Double-layer Polyelectrolyte Microspheres. [J]. Acta Polymerica Sinica 0(7):900-908(2018)
Dan Wang, Li-jie Luo, Gao-long Wu, Bin Liu, Yong-jun Chen, Xin-lin Yang. Preparation and Charecterization of Charged Hollow Double-layer Polyelectrolyte Microspheres. [J]. Acta Polymerica Sinica 0(7):900-908(2018) DOI： 10.11777/j.issn1000-3304.2018.18028.
摘要
结合溶胶-凝胶法和蒸馏沉淀聚合法，合成了二氧化硅/阴离子聚合物/二氧化硅/阴离子聚合物和二氧化硅/阴离子聚合物/二氧化硅/阳离子聚合物四层复合微球(阴离子聚合物为聚(乙二醇二甲基丙烯酸酯-
co
-甲基丙烯酸)；阳离子聚合物为聚(二乙烯基苯-
co
-对乙烯基苄氯吡啶盐)). 通过选择性移除二氧化硅内核和三明治夹心层，分别制备得到相应的内外都带负电荷以及内外带有相反电荷的两性双层空心聚电解质微球. 考察了阳离子聚合物层的合成过程中，不同DVB在单体中的含量对其壳层厚度和双层聚电解质微球的电荷的影响，使用透射电镜(TEM)、红外光谱(FTIR)和zeta电位仪分别对空心聚电解质微球的形态、化学组成和电荷性进行了表征. 结果表明了在蒸馏沉淀聚合过程中，通过调节二乙烯基苯交联剂在整个单体中的用量(30% ~ 60%)，可调控具有相反电荷的两性空心聚合物微球的表面电位 (8.82 ~ 39.82 mV).
Abstract
Monodisperse tetra-layer hybrid microspheres
the types of SiO
2
/anionic polymer/SiO
2
/anionic polymer and SiO
2
/anionic polymer/SiO
2
/cationic polymer
were prepared by a four-step synthetic procedure. The hollow double-shelled electrolyte microspheres
with either anionic species (−41.43 ~ −54.65 mV) on both shells or zwitterionic structures on the inner and outer shells
were prepared
via
combination of distillation precipitation polymerization and sol-gel method for the preparation of the tetra-layer inorganic/polymer hybrid microspheres together with the subsequently selective removal of silica core and sandwiched layer. In such a process
the modified Stöber sol-gel technique was utilized for synthesis of silica inner core and the sandwiched third layer for these tetra-layer inorganic/polymer hybrid microspheres. The P(EGDMA-
co
-MAA) and P(DVB-
co
-St) polymeric layers were synthesized
via
the radical capture of EGDMA/MAA and DVB/St comonomers as well as their
co
-oligomers from the vinyl groups as the reactive sites with presence of the 3-(methacryloxy)propyl trimethoxysilane (MPS) silica nanoparticles as the seeds during the distillation precipitation polymerization. The outer P(DVB-
co
-StMPPy
+
Cl
−
) shell was further developed by a surface pyridinium reaction between the chloromethyl group on the surface of polymer network and the pyridine
via
suspension of SiO
2
/P(EGDMA-
co
-MAA)/SiO
2
/P(DVB-
co
-St) tetra-layer microspheres with various DVB crosslinking degrees (30 vol%
50 vol% and 60 vol%) in pyridine. Transmission electron microscopy (TEM)
Fourier transfer infrared spectra (FTIR) and zeta potential were systematically used for characterization of the morphology
chemical components and surface charges of these hollow double-layer polyelectrolyte microspheres. The resultant multi-layer inorganic silica/polymer multi-layer hybrid microspheres had smooth surface with regular shape with efficient interaction between the polymer layer and the inorganic species. The shape of the polymeric shells were deformed in the hollow polyelectrolyte microspheres due to shrinkage and collapse of the shells when they were slightly crosslinked. The thicknesses (12 − 59 nm) and zeta-potentials (8.82 − 39.82 mV) of the polymeric shell-layer can be facilely adjusted by changing the amount of DVB crosslinker in the comonomers (0.30 − 0.60) in the synthesis. The hollow double polymer electrolyte microspheres have great potential for applications as the active components in the field of methanol fuel cell for water reservoirs with high proton conductivity due to its huge cavities and zwitter-ionic channels for electron conductivity.
关键词
聚电解质微球空心微球双层聚合物微球蒸馏沉淀聚合
Keywords
Polyelectrolyte microsphereHollow double-shell microsphereZwitterionic polymer microsphereDistillation precipitation polymerization
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