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
1. [1]
  Cui J W, Wang Y J, Postma A, Hao J C, Hosta-Rigau L, Caruso F. Adv Funct Mater, 2010, 20(10):1625-1631 doi: 10.1002/adfm.v20:10
2. [2]
  Liu S Y, WeaverJ V M, Save M, Armes S P. Langmuir, 2002, 18(22):1347-1353
3. [3]
  Torchilin V P, Frank-Kamenetsky M D, Wolf G L. Acad Radiol, 1999, 6(1):61-65 doi: 10.1016/S1076-6332(99)80063-4
4. [4]
  Xiao L F, Cao Y L, Xiao J, Schwenzer B, Engelhard M H, Saraf L V, Nie Z M, ExarhosG J, Liu J. Adv Mater, 2012, 24(9):1176-1181 doi: 10.1002/adma.v24.9
5. [5]
  Zha L S, Zhang Y, Yang W L, Fu S K. Adv Mater, 2002, 14(15):1090-1092 doi: 10.1002/1521-4095(20020805)14:15<1090::AID-ADMA1090>3.0.CO;2-6
6. [6]
  Bae Y, Nishiyama N, Fukushima S, Koyama H, Yasuhiro M, Kataoka K. Bioconjug Chem, 2005, 16(1):131-138 doi: 10.1021/bc034049g
7. [7]
  Wu H, Zhu L, Torchilin V P. Biomaterials, 2013, 34(4):1213-1222 doi: 10.1016/j.biomaterials.2012.08.072
8. [8]
  Fernández-Argüelles M T, Yakovlev A, Sperling R A, Luccardini C, Gaillard S, Medel A S, Mallet J M, Brochon J C, Feltz A, Oheim M, Parak W J.Nano Lett, 2007, 7(9):2613-2617 doi: 10.1021/nl070971d
9. [9]
  Wang Wei, Jin Zhaohui, Li Tielong. China Environmental Science, 2009, 29(8):811-815
10. [10]
  Guo M, Mao H, Li Y, Zhu A, He H, Yang H, Wang Y, Tian X, Ge C, Peng Q, Wang X, Yang X, Chen X, Liu G, Chen H. Biomaterials, 2014, 35(16):4656-4666 doi: 10.1016/j.biomaterials.2014.02.018
11. [11]
  Li Nan, Wang Xiaogong. Acta Polymerica Sinica, 2013, (4):549-555
12. [12]
  Blomberg S, Ostberg S, Harth E, Bosman A W, vanHorn B, HawkerC J. J Polym Sci, Part A:Polym Chem, 2002, 40(9):1309-1320 doi: 10.1002/(ISSN)1099-0518
13. [13]
  Morinaga T, Ohkura M, Ohno K, Tsujii Y, Fukuda T. Macromolecules, 2007, 40(4):1159-1164 doi: 10.1021/ma062230p
14. [14]
  Huang X, Appelhans D, Formanek P, Simon F, Voit B. Macromolecules, 2011, 44(21):8351-8360 doi: 10.1021/ma201982f
15. [15]
  Ali S I, Heuts J P, van Herk A M. Langmuir, 2010, 26(11):7848-7858 doi: 10.1021/la904709c
16. [16]
  Ali S I, Heuts J P, van Herk A M. Soft Matter, 2011, 7(11):5382-5390 doi: 10.1039/c1sm05266g
17. [17]
  Städler B, Chandrawati R, Goldie K, Caruso F. Langmuir, 2009, 25(12):6725-6732 doi: 10.1021/la900213a
18. [18]
  Huang B, Bai F, Yang X L, HuangW Q. Chinese J Polym Sci, 2010, 28(2):277-285 doi: 10.1007/s10118-010-9089-7
19. [19]
  Liu W, Yang X L, He X G. Chinese J Polym Sci, 2009, 27(2):275-284 doi: 10.1142/S025676790900390X
20. [20]
  Jiang Y M, Li B T, Deng W, LiX Y, KanC Y. Chinese J Polym Sci, 2014, 32(1):21-28 doi: 10.1007/s10118-014-1391-3
21. [21]
  Jiang Y M, Li B T, Wang W J, Xu M, Kan C Y. Chinese J Polym Sci, 2014, 32(2):177-186 doi: 10.1007/s10118-014-1387-z
22. [22]
  Fang Yingjun, Deng Wei, Zuo Han, Kan Chengyou. Acta Polymerica Sinica, 2015, (8):927-932
23. [23]
  Ni K F, Shan G R, Weng Z X. Macromolecules, 2006, 39(7):2529-2535 doi: 10.1021/ma052061t
24. [24]
  Jang J, Lee K. Chem Commun, 2002, 10(10):1098-1099
25. [25]
  Tiarks F, Landfester K, Antonietti M. Langmuir, 2001, 17(3):908-918 doi: 10.1021/la001276n
26. [26]
  Lu F, Luo Y, Li B. Macromol Rapid Commun, 2010, 28(28):868-874
27. [27]
  Fuchs A V, Thurecht K J. Macromol Chem Phys, 2015, 216(12):1271-1281 doi: 10.1002/macp.201500061
28. [28]
  Ye C, Luo Y, Liu X. Polymer, 2011, 52(3):683-693 doi: 10.1016/j.polymer.2010.12.030
29. [29]
  Otsu T, Yoshida M. Makromo Chem, Rapid Commun, 2003, 3(2):127-132
30. [30]
  Chen X P, Qiu K Y. Chem Commun, 2000, 3(3):233-234
31. [31]
  Li P, Qiu K Y. J Polym Sci, Part A:Polym Chem, 2002, 40(12):2093-2097 doi: 10.1002/(ISSN)1099-0518
32. [32]
  Li P, Qin S H, Qin D Q, Qiu K Y. Polym Int, 2004, 53(6):756-765 doi: 10.1002/(ISSN)1097-0126
33. [33]
  Zhang W, Zhou N, Zhu J, Sun B, Zhu X. J Polym Sci, Part A:Polym Chem, 2006, 44(1):510-518 doi: 10.1002/(ISSN)1099-0518
34. [34]
  Zhang W, Zhu X, Zhu J, Chen J. J Polym Sci, Part A:Polym Chem, 2006, 44(1):32-41 doi: 10.1002/(ISSN)1099-0518
35. [35]
  Nicolaÿ R, Kwak Y, Matyjaszewski K. Macromolecules, 2008, 41(13):4585-4596 doi: 10.1021/ma800539v
36. [36]
  Blomberg S, Ostberg S, Harth E, Bosman A W, van Horn B, Hawker C J, Zhang Y Z, Schröder K, Kwak Y, Krys P, Morin A N, Pintauer T, Poli R, Matyjaszewski K. Macromolecules, 2013, 46(46):5512-5519
37. [37]
  Jiang H J, Zhang L F, Jiang X W, Bao X G, Cheng Z P, Zhu X L. Macromol Rapid Commun, 2014, 35(15):1332-1339 doi: 10.1002/marc.v35.15
38. [38]
  Jiang H J, Tian C, Zhang L F, Cheng Z P, Zhu X L. RSC Adv, 2014, 4(94):52430-52437 doi: 10.1039/C4RA09439E
39. [39]
  Jing X, Liu F, Yang X, Ling P, Li L, Long C, Li A. J Hazard Mater, 2009, 167(1-3):589-596 doi: 10.1016/j.jhazmat.2009.01.020
40. [40]
  Otsu T, Yoshida M. Macromol Rapid Commun, 1982, 3(2):127-132 doi: 10.1002/marc.1982.030030208
41. [41]
  Otsu T, Matsumoto A. Adv Polym Sci, 1998, 136:74-137
1. [1]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
2. [2]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
3. [3]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
4. [4]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
5. [5]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
6. [6]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
7. [7]
  Xuefei Leng , Yanshai Wang , Hai Wang , Shengyang Tao . The In-Depth integration of “Industry-University-Research” in the Exploration and Practice of “Comprehensive Training in Polymer Engineering”. University Chemistry, 2025, 40(4): 66-71. doi: 10.12461/PKU.DXHX202405105
8. [8]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
9. [9]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
10. [10]
  Xingchao Zhao , Xiaoming Li , Ming Liu , Zijin Zhao , Kaixuan Yang , Pengtian Liu , Haolan Zhang , Jintai Li , Xiaoling Ma , Qi Yao , Yanming Sun , Fujun Zhang . 倍增型全聚合物光电探测器及其在光电容积描记传感器上的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2311021-. doi: 10.3866/PKU.WHXB202311021
11. [11]
  Fanpeng Meng , Fei Zhao , Jingkai Lin , Jinsheng Zhao , Huayang Zhang , Shaobin Wang . 优化氮化碳纳米片/球形共轭聚合物S型异质结界面电场以促进析氢反应. Acta Physico-Chimica Sinica, 2025, 41(8): 100095-. doi: 10.1016/j.actphy.2025.100095
12. [12]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125
13. [13]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
14. [14]
  .
  南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积
  . CCS Chemistry, 2025, 7(0): -.
15. [15]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
16. [16]
  Xiaoli Sun , Xiang Wu , Li Gan , Wenming Wan . Barbier Polymerization: A New Teaching Case for Step-Growth Polymerization. University Chemistry, 2025, 40(4): 113-118. doi: 10.12461/PKU.DXHX202406102
17. [17]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
18. [18]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
19. [19]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
20. [20]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(205)
HTML views(17)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Preparation of Hollow Nanospheres by Miniemulsion Polymerization

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

Metrics

通讯作者: 陈斌, bchen63@163.com