细乳液聚合法制备聚合物空心球

张珂; 汪太生; 李自力; 戴静闻; 何卫东; 白如科

doi:10.11777/j.issn1000-3304.2017.17231

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细乳液聚合法制备聚合物空心球

研究论文 | 更新时间：2021-01-26

- 细乳液聚合法制备聚合物空心球
- Preparation of Hollow Nanospheres by Miniemulsion Polymerization
- 高分子学报 2018年第4期页码：475-481
- 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：
  
  何卫东, E-mail: wdhe@ustc.edu.cn Wei-dong He, E-mail: wdhe@ustc.edu.cn
  白如科, E-mail:bairk@ustc.edu.cn Ru-ke Bai, E-mail: bairk@ustc.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.17231
  中图分类号：
- 纸质出版日期：2018-4-20，
  
  收稿日期：2017-4-1，
  
  修回日期：2017-4-23，
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张珂, 汪太生, 李自力, 戴静闻, 何卫东, 白如科. 细乳液聚合法制备聚合物空心球[J]. 高分子学报, 2018,(4):475-481.

Ke Zhang, Tai-sheng Wang, Zi-li Li, Jing-wen Dai, Wei-dong He, Ru-ke Bai. Preparation of Hollow Nanospheres by Miniemulsion Polymerization[J]. Acta Polymerica Sinica, 2018,(4):475-481.
张珂, 汪太生, 李自力, 戴静闻, 何卫东, 白如科. 细乳液聚合法制备聚合物空心球[J]. 高分子学报, 2018,(4):475-481. DOI： 10.11777/j.issn1000-3304.2017.17231.

Ke Zhang, Tai-sheng Wang, Zi-li Li, Jing-wen Dai, Wei-dong He, Ru-ke Bai. Preparation of Hollow Nanospheres by Miniemulsion Polymerization[J]. Acta Polymerica Sinica, 2018,(4):475-481. DOI： 10.11777/j.issn1000-3304.2017.17231.

摘要

设计、合成了一种两亲性的引发转移终止剂（inifeter），2-（

，

-二羧甲基二硫代氨基甲酸酯基）异丁酸十二酯（DIBDC），通过核磁谱对其结构进行了表征.DIBDC既可引发聚合，又是表面活性剂.以DIBDC作为乳化剂，醋酸铜（Cu（OAc）

）为催化剂，进行了细乳液聚合法制备聚合物空心球的研究.实验结果表明，通过细乳液聚合，制备了直径为100~200 nm的聚苯乙烯空心球.由于DIBDC中的二硫代氨基甲酸酯基团与卤素在化学行为上相似，因此，DIBDC可作为假卤素引发剂，在Cu（OAc）

催化作用下产生自由基，从而引发聚合反应.Cu（OAc）

存在于水相中，可以扩散到油水界面层与DIBDC作用，而活性自由基增长链始终处于油水界面，因此，聚合反应只能在油水界面层的"受限空间"内进行，从原理上避免了实心聚合物球的形成.

Abstract

An amphiphilic iniferter

2-(

-dicarboxymethyl dithiocarbamate) dodecyl isobutyrate (DIBDC)

was synthesized and characterized by

H-NMR spectroscopy. Dodecyl 2-bromo-2-methylpropionate was prepared from lauryl alcohol and 2-bromo-2-methylpropionyl bromide in the presence of triethylamine in ice water bath. Sodium

-dicarboxymethyl dithiocarbamate was synthesized from iminodiacetic acid

carbon disulfide and sodium hydroxide at room temperature. DIBDC was synthesized by the reaction between dodecyl 2-bromo-2-methylpropionate and sodium

-dicarboxymethyl dithiocarbamate at 60℃. Since DIBDC is not only a surfactant

but also used as an initiator

miniemulsion polymerization of styrene was performed in the presence of DIBDC using Cu(OAc)

as the catalyst. The miniemulsion systemconsisted of distilled water

surfactant

hexadecane and styrene. Stable miniemulsion was obtained after stirring and ultrasonic treatment. After adding copper acetate and heating up to 80℃

the polymerization began.To characterize the hollow spheres

dynamic light scattering (DLS)

scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used. The results indicated that hollow polystyrene nanospheres with diameters of 100 nm to 200 nm were successfully prepared by the living radical miniemulsion polymerization. The PDI of diameter was below 0.1

showing good monodispersity of the nanospheres. It is well known that dithiocarbamates act as pseudohalogens

therefore

DIBDC can be used to perform a living radical polymerization

which is similar to atom transfer radical polymerization under catalysis of Cu(OAc)

. Due to the amphiphilicity of DIBDC and the reversible equilibrium between the active and the dormant species

thepolymerization was realized in aconfinedspace of the oil-water interface. As a result

hollow nanospheres were formed. And moreover

the formation of solid polymer nanoparticles was avoided. However

when azobisisobutyronitrile (AIBN) was used as the initiator instead of Cu(OAc)

as a catalyst

solid polystyrene nanospheres were obtained. The reason is that the polymerization is no longer carried out in the confined space

which is similar to suspension polymerization because AIBN is dissolved in the micelles.

关键词

超引发转移终止剂活性自由基聚合细乳液聚合聚合物空心球

Keywords

IniferterLiving radical polymerizationMiniemulsion polymerizationHollow polymer spheres

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