聚合物模板微球表面电性对中空二氧化硅微球形貌的影响

段国伟; 谢李昭; 赵驰; 汪谟贞; 葛学武

doi:10.11777/j.issn1000-3304.2017.16257

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聚合物模板微球表面电性对中空二氧化硅微球形貌的影响

研究论文 | 更新时间：2021-03-19

- 聚合物模板微球表面电性对中空二氧化硅微球形貌的影响
- Influence of the Surface Electrical Property of Polymer Template Microspheres on the Morphology of Hollow Silica Microspheres
- 高分子学报 2017年第5期页码：785-792
- 作者机构：
  
  中国科学院软物质化学重点实验室中国科学技术大学高分子科学与工程系合肥 230026
- 作者简介：
  
  葛学武, E-mail:xwge@ustc.edu.cn Xue-wu Ge, E-mail:xwge@ustc.edu.cn
- 基金信息：
  
  国家自然科学基金(51473152);国家自然科学基金(51573174);中央高校基本科研业务费专项资金(WK2060200012);中央高校基本科研业务费专项资金(WK3450000001)
- DOI：10.11777/j.issn1000-3304.2017.16257
  中图分类号：
- 纸质出版日期：2017-5，
  
  收稿日期：2016-8-18，
  
  修回日期：2016-9-28，
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段国伟, 谢李昭, 赵驰, 汪谟贞, 葛学武. 聚合物模板微球表面电性对中空二氧化硅微球形貌的影响[J]. 高分子学报, 2017,(5):785-792.

Guo-wei Duan, Li-zhao Xie, Chi Zhao, Mo-zhen Wang, Xue-wu Ge. Influence of the Surface Electrical Property of Polymer Template Microspheres on the Morphology of Hollow Silica Microspheres[J]. Acta Polymerica Sinica, 2017,(5):785-792.
段国伟, 谢李昭, 赵驰, 汪谟贞, 葛学武. 聚合物模板微球表面电性对中空二氧化硅微球形貌的影响[J]. 高分子学报, 2017,(5):785-792. DOI： 10.11777/j.issn1000-3304.2017.16257.

Guo-wei Duan, Li-zhao Xie, Chi Zhao, Mo-zhen Wang, Xue-wu Ge. Influence of the Surface Electrical Property of Polymer Template Microspheres on the Morphology of Hollow Silica Microspheres[J]. Acta Polymerica Sinica, 2017,(5):785-792. DOI： 10.11777/j.issn1000-3304.2017.16257.

摘要

分别以过硫酸钾和偶氮二异丁基脒盐酸盐为引发剂，以聚乙烯吡咯烷酮（PVP）为分散剂，在水中引发苯乙烯聚合制备了2种表面分别带负电性和正电性基团的聚苯乙烯（PS）模板微球.在氨水催化下，利用正硅酸乙酯的水解缩合，形成PS/SiO

复合微球，去除模板后得到中空SiO

微球，并对其进行FTIR、电子显微镜、TGA以及氮气吸附等分析表征.结果表明，PS模板微球表面的电性决定了OH

的分布，从而导致PS模板微球表面SiO

壳层不同的形成机制.当以表面带负电的PS微球为模板时，可得到树莓状的中空SiO

微球；而以表面带正电的PS微球为模板时，得到是表面光滑的，具有介孔结构的中空SiO

微球.

Abstract

We prepared two kinds of monodispersed polystyrene (PS) microspheres with different surface electrical properties from the polymerization of styrene in water using different initiators. The PS microspheres prepared with potassium persulfate (KPS) as the initiator (PS-a) have negative zeta potential in water

and those prepared with 2

2'-azobis (2-methylpropionamidine) dihydrochloride (AIBA) as the initiator (PS-c) have positive zeta potential in water. Next

PS-a and PS-c microspheres were respectively used as the templates to prepare hollow SiO

microspheres through a sol-gel process of tetraethoxysilane (TEOS) in an ethanol/ammonia medium. Based on the analysis on the products by FTIR

SEM

TEM

TGA

and N

adsorption-desorption isotherms

it was found that the distribution of OH

in the system depended on the surface electrical property of the PS template microspheres

which would lead to different formation processes of the silica shell on the template microspheres. When the PS-a microspheres were used as the template

the OH

ions were repulsed from the negative surface of the PS-a template microspheres

due to the electrostatic repulsion interaction. Thus

the SiO

nanoparticles with a size of several tens of nanometers were firstly formed by hydrolysis and condensation of TEOS in the medium

and then adsorbed and packed on the surface of PS-a template microspheres through the polar interaction

resulting in the formation of a raspberry-like silica shell with macropores. After the PS-a template microspheres etched by toluene

the raspberry-like hollow silica microspheres were obtained. However

when PS-c template microspheres were used as the template

the OH

ions were adsorbed on the positive surface of the template microspheres. Then

a smooth and dense silica layer was grown directly from the surface of the template microspheres through the hydrolysis and the condensation of TEOS catalyzed by the adsorbed OH

ions. After calcination at 600℃ for 8 h

hollow silica microspheres with a smooth and mesoporous silica shell were produced. This work indicates that the morphology of the hollow silica microspheres can be controlled through the surface electrical property of the template microspheres. This study may lead to more applications of hollow silica microspheres in the area of control-release materials

drug carriers

and absorbents.

关键词

中空微球二氧化硅聚苯乙烯模板微球表面电性正硅酸乙酯

Keywords

Hollow microspheresSilicaPolystyrene template microspheresSurface electrical propertyTetraethoxysilane

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