Citation: Hao-yu Yu, Jian-wei Shao, Dong Chen, Shi-chao Wang, Li Wang, Wan-tai Yang. Synthesis of Thioether Compounds and Their Application in Initiating/Controlling the Radical Polymerization of Styrene[J]. Acta Polymerica Sinica, ;2018, 0(11): 1422-1429. doi: 10.11777/j.issn1000-3304.2018.18107 shu

Synthesis of Thioether Compounds and Their Application in Initiating/Controlling the Radical Polymerization of Styrene

College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Li Wang, lwang@mail.buct.edu.cn Wan-tai Yang, yangwt@mail.buct.edu.cn
Received Date: 17 April 2018
Revised Date: 9 May 2018
Available Online: 17 July 2018

With inspiration from the structure of macromolecular thioether generated in the 9H-xanthene-9-thione mediated radical polymerization, five thioethers containing 9-alkyl-9-phenylthio/methylthio-xanthene structure were synthesized. Xanthydrol was selected as the precursor for two 9-substituted xanthene intermediates. 9-(Phenylthio)-9H-xanthene was obtained via a condensation reaction between xanthydrol and thiophenol in the presence of perchloric acid as catalyst. 9-(Methylthio)-9H-xanthene was obtained via the thioetherification of the chlorinated product of xanthydrol with sodium methyl mercaptide. The sulfurated intermediates were deprotonated by n-butyl lithium, and transformed into five target products via substitution reactions with three alkyl halides individually. ¹H-NMR, ¹³C-NMR, FTIR and UV-Vis analyses were conducted to confirm and characterize the thioethers. Afterwards, a systematic study on the polymerization behavior of styrene (St) initiated by the thioethers was carried out in the absence and presence of a thermal initiator. Bulk polymerizations of St were initiated successfully by the thioethers at 80 °C with relatively low monomer conversions, and the reactions exhibited uncontrolled polymerization behaviors without obvious increase in number-average molecular weight (M_n) in the polymerization process with the PDI of polymeric products above 3.0. However, when the thioethers were used together with 2,2'-azobis(2,4-dimethyl)valeronitrile (ABVN) in the solution polymerization of St in toluene at 65 °C, higher monomer conversions compared with those of bulk polymerization and certain controllability could be achieved, reflected by a linear increase in M_n with conversion. Besides, the effects of molar ratio of ABVN to thioether and reaction temperature on the polymerization behavior of St were investigated in detail. A reduction in the molar ratio of ABVN to thioether would cause a reduction in the concentration of propagating radicals, and lead to a decrease in monomer conversion. But the PDI of polymeric product narrowed down indicating a controllable polymerization. Furthermore, elevated reaction temperature brought about an increased concentration of chain radical, and resulted in a relatively low M_n with a broadened PDI.
- Controlled radical polymerization,
- Thioether,
- Styrene,
- Bulk polymerization,
- Solution polymerization
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