Citation: Xiao-qian Zhang, Xuan Zhou, Ying-juan Sun, Li-na Yue, Yong-xiang Shi, Ke Xu, Zi-xi Luo, Yi-bo Wu. Cationic Polymerization of p-Methylstyrene in Ionic Lquids Media[J]. Acta Polymerica Sinica, ;2019, 50(4): 375-383. doi: 10.11777/j.issn1000-3304.2018.18239 shu

Cationic Polymerization of p-Methylstyrene in Ionic Lquids Media

Xiao-qian Zhang ^1,, ,
Xuan Zhou ¹ ,
Ying-juan Sun ¹ ,
Li-na Yue ¹ ,
Yong-xiang Shi ¹ ,
Ke Xu ¹ ,
Zi-xi Luo ¹ ,
Yi-bo Wu ^2,,

1.
Department of Environmental Engineering, North China Institute of Science and Technology, Langfang 065201
2.
Beijing Key Lab of Special Elastomer Composite Materials, Beijing Institute of Petrochemical Technology, Beijing 102617

Corresponding author: Xiao-qian Zhang, zxqphd@163.com Yi-bo Wu, wuyibo@bipt.edu.cn
Received Date: 9 November 2018
Revised Date: 17 November 2018
Available Online: 14 December 2018

In this study, cationic polymerization of p-methylstyrene (p-MeSt) was studied in ionic liquid (IL) reaction media. The effects of ILs on p-MeSt cationic polymerization were analyzed through density functional theory (DFT) and experimental method. The influences of various initiating systems on p-MeSt cationic polymerization were investigated, and the efficiencies of various ILs as reaction solvents were discussed. The structure of the polymerization product was characterized through ¹H-NMR and FTIR characterization analyses; number-average molecular weight (M_n) and molecular weight distribution were measured through gel permeation chromatography (GPC); a temperature recorder tracked the relationship between polymerization system temperature variation and reaction time. The results showed that a CumOH(2-phenyl-2-propanol)/BF₃·OEt₂ initiating system is relatively effective in IL media over those frequently used in cationic polymerization reactions. The products polymerized in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][NTf₂]) IL media have higher molecular weight and yield (up to 99%) and narrower molecular weight distribution (M_w/M_n is ~ 2.0) than those in traditional molecular solvents (such as CH₂Cl₂). An analysis of the effects of ILs on polymerization indicated that ILs act as inert solvents in p-MeSt cationic polymerization and do not directly participate in the polymerization reaction. The ionic environment of IL cannot inhibit a chain transfer reaction completely, but can stabilize active species and disperse positive charges. Thus, the polymerization reaction is milder in IL media than that in traditional molecular solvents. The results of IL recovery and reuse showed that these solvents can be used as reaction medium over a number of cycles without remarkable influence on the products. Finally, the corresponding elementary reaction mechanism of the cationic polymerization of p-MeSt initiated by the CumOH/BF₃·OEt₂ system in [Bmim][NTf₂] IL media was proposed in this study. As is known, ILs are recyclable and environmentally friendly green solvents. This study expands the reaction solvent of cationic polymerization and promotes the development of green chemistry.
- Cationic polymerization,
- Ionic liquids,
- p-Methylstyrene,
- Polymerization mechanism,
- Green solvents
1. [1]
  Figoli A, Marino T, Simone S, Di Nicolo E, Li X M, He T, Tornaghi S, Drioli E. Green Chem, 2014, 16(9): 4034 − 4059 doi: 10.1039/C4GC00613E
2. [2]
  Cevasco G, Chiappe C. Green Chem, 2014, 16(5): 2375 − 2385 doi: 10.1039/c3gc42096e
3. [3]
  Adawiyah N, Moniruzzaman M, Hawatulailaa S, Goto M. Med Chem Commun, 2016, 7: 1881 − 1897 doi: 10.1039/C6MD00358C
4. [4]
  Mallakpour S, Rafiee Z. J Polym Environ, 2011, 19(2): 447 − 484 doi: 10.1007/s10924-011-0287-3
5. [5]
6. [6]
  Anastasaki A, Nikolaou V, Nurumbetov G, Truong N P, Pappas G S, Engelis N G, Quinn J F, Whittaker M R, Davis T P, Haddleton D M. Macromolecules, 2015, 48(15): 5140 − 5147 doi: 10.1021/acs.macromol.5b01192
7. [7]
  Harrisson S, Mackenzie S R, Haddleton D M. Macromolecules, 2003, 36(14): 5072 − 5075 doi: 10.1021/ma034447e
8. [8]
  Liu X H, Zhu Q, Zhang Y G, Zhang Q Y, Ding C, Li J. RSC Adv, 2017, 7(71): 45022 − 45028 doi: 10.1039/C7RA09154K
9. [9]
  Lozinskaya E I, Shaplov A S, Vygodskii Y S. Eur Polym J, 2004, 40(9): 2065 − 2075 doi: 10.1016/j.eurpolymj.2004.05.010
10. [10]
  Biedroń T, Kubisa P. J Polym Sci, Part A: Polym Chem, 2007, 45(17): 4168 − 4172 doi: 10.1002/(ISSN)1099-0518
11. [11]
  Kokubo H, Watanabe M. Polym Adv Technol, 2008, 19(10): 1441 − 1444 doi: 10.1002/pat.v19:10
12. [12]
  Vijayaraghavan R, MacFarlane D. Chem Commun, 2004, (6): 700 − 701 doi: 10.1039/b315100j
13. [13]
  Baśko M, Biedroń T, Kubisa P. J Polym Sci, Part A: Polym Chem, 2009, 47(20): 5251 − 5257 doi: 10.1002/pola.v47:20
14. [14]
  Yoshimitsu H, Kanazawa A, Kanaoka S, Aoshima S. J Polym Sci, Part A: Polym Chem, 2016, 54(12): 1774 − 1784 doi: 10.1002/pola.28039
15. [15]
  Singha N K, Hong K, Mays J W. RSC Smart Mater, 2017: 1 − 22
16. [16]
17. [17]
  de P, Faust R. Macromolecules, 2005, 38(13): 5498 − 5505 doi: 10.1021/ma050449i
18. [18]
  Malhotra S, Lessard P, Minh L, Hard L B. J Macromol Sci-Chem, 1980, 14(4): 517 − 540 doi: 10.1080/00222338008081033
19. [19]
  Luda M P, Guaita M, Chiantore O. Makromol Chem Macromol Symp, 1989, 25: 101 − 116 doi: 10.1002/(ISSN)1521-3900a
20. [20]
  Satoh K, Nakashima J, Kamigaito M, Sawamoto M. Macromolecules, 2001, 34(3): 396 − 401 doi: 10.1021/ma0006070
21. [21]
  Lutz J F, Matyjaszewski K. J Polym Sci, Part A: Polym Chem, 2005, 43(4): 897 − 910 doi: 10.1002/(ISSN)1099-0518
22. [22]
  Vasilenko I V, Kostjuk S V, Kaputsky F N, Nedorezova P M, Aladyshev A M. Macromol Chem Phys, 2008, 209(12): 1255 − 1265 doi: 10.1002/(ISSN)1521-3935
23. [23]
  Kostjuk S V, Radchenko A V, Ganachaud F. Macromolecules, 2007, 40(3): 482 − 490 doi: 10.1021/ma062261k
24. [24]
1. [1]
  Nengmin ZHU , Wenhao ZHU , Xiaoyao YIN , Songzhi ZHENG , Hao LI , Zeyuan WANG , Wenhao WEI , Xuanheng CHEN , Weihai SUN . Preparation of high-performance CsPbBr₃ perovskite solar cells by the aqueous solution solvent method. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1131-1140. doi: 10.11862/CJIC.20240419
2. [2]
  Zeyi Yan , Ruitao Liu , Xinyu Qi , Yuxiang Zhang , Lulu Sun , Xiangyuan Li , Anchao Feng . Exploration of Suspension Polymerization: Preparation and Fluorescence Stability of Perovskite Polystyrene Microbeads. University Chemistry, 2025, 40(4): 72-79. doi: 10.12461/PKU.DXHX202405110
3. [3]
  Wenjun Zheng . Application in Inorganic Synthesis of Ionic Liquids. University Chemistry, 2024, 39(8): 163-168. doi: 10.3866/PKU.DXHX202401020
4. [4]
  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
5. [5]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
6. [6]
  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
7. [7]
  Li'na ZHONG , Jingling CHEN , Qinghua ZHAO . Synthesis of multi-responsive carbon quantum dots from green carbon sources for detection of iron ions and L-ascorbic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 709-718. doi: 10.11862/CJIC.20240280
8. [8]
  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
9. [9]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
10. [10]
  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
11. [11]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
12. [12]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-. doi: 10.3866/PKU.WHXB202406014
13. [13]
  Pingping LU , Shuguang ZHANG , Peipei ZHANG , Aiyun NI . Preparation of zinc sulfate open frameworks based probe materials and detection of Pb²⁺ and Fe³⁺ ions. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 959-968. doi: 10.11862/CJIC.20240411
14. [14]
  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
15. [15]
  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
16. [16]
  Guoze Yan , Bin Zuo , Shaoqing Liu , Tao Wang , Ruoyu Wang , Jinyang Bao , Zhongzhou Zhao , Feifei Chu , Zhengtong Li , Yusuke Yamauchi , Saad Melhi , Xingtao Xu . Opportunities and Challenges of Capacitive Deionization for Uranium Extraction from Seawater. Acta Physico-Chimica Sinica, 2025, 41(4): 100032-. doi: 10.3866/PKU.WHXB202404006
17. [17]
  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
18. [18]
  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
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(111)
HTML views(9)

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