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
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