Citation: 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 shu

Preparation of Hollow Nanospheres by Miniemulsion Polymerization

Chinese Academy of Sciences Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026

Corresponding author: Wei-dong He, wdhe@ustc.edu.cn Ru-ke Bai, bairk@ustc.edu.cn
Received Date: 1 April 2017
Revised Date: 23 April 2017

An amphiphilic iniferter, 2-(N, N-dicarboxymethyl dithiocarbamate) dodecyl isobutyrate (DIBDC), was synthesized and characterized by ¹H-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 N, N-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 N, N-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)₂ 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)₂. 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)₂ 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.
- Iniferter,
- Living radical polymerization,
- Miniemulsion polymerization,
- Hollow polymer spheres
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