基于氧杂蒽结构的硫醚化合物的设计合成及引发/调控苯乙烯自由基聚合的研究

于昊宇; 邵健为; 陈冬; 王世超; 王力; 杨万泰

doi:10.11777/j.issn1000-3304.2018.18107

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基于氧杂蒽结构的硫醚化合物的设计合成及引发/调控苯乙烯自由基聚合的研究

研究论文 | 更新时间：2021-01-26

- 基于氧杂蒽结构的硫醚化合物的设计合成及引发/调控苯乙烯自由基聚合的研究
- Synthesis of Thioether Compounds and Their Application in Initiating/Controlling the Radical Polymerization of Styrene
- 高分子学报 2018年0卷第11期页码：1422-1429
- 作者机构：
  
  北京化工大学材料科学与工程学院　北京 100029
- 作者简介：
  
  E-mail: lwang@mail.buct.edu.cn Li Wang, E-mail: lwang@mail.buct.edu.cn
  E-mail: yangwt@mail.buct.edu.cn Wantai Yang, E-mail: yangwt@mail.buct.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21404004，21474006)资助项目()
- DOI：10.11777/j.issn1000-3304.2018.18107
  中图分类号：
- 纸质出版日期：2018-11，
  
  收稿日期：2018-4-17，
  
  修回日期：2018-5-9，
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于昊宇, 邵健为, 陈冬, 王世超, 王力, 杨万泰. 基于氧杂蒽结构的硫醚化合物的设计合成及引发/调控苯乙烯自由基聚合的研究[J]. 高分子学报, 2018,0(11):1422-1429.

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.
于昊宇, 邵健为, 陈冬, 王世超, 王力, 杨万泰. 基于氧杂蒽结构的硫醚化合物的设计合成及引发/调控苯乙烯自由基聚合的研究[J]. 高分子学报, 2018,0(11):1422-1429. DOI： 10.11777/j.issn1000-3304.2018.18107.

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.

摘要

讨论了5种含有氧杂蒽结构的硫醚化合物的合成过程. 以占吨醇为起始原料，通过高氯酸催化其与苯硫酚缩合制备苯硫醚，通过对占吨醇氯代并与甲硫醇钠反应制备甲硫醚，2条路径最终均通过正丁基锂拔氢和烷基化反应得到目标产物. 通过核磁共振(

H-NMR、

C-NMR)、傅里叶红外光谱(FTIR)和紫外可见吸收光谱(UV-Vis)手段对5种硫醚进行表征和结构确认. 系统研究了硫醚化合物单独使用及其与传统引发剂共用时的苯乙烯(St)自由基聚合行为. 80 °C下，硫醚化合物均能引发St的本体聚合，但聚合转化率低且表现出不受控的普通自由基聚合行为. 而当将硫醚化合物与偶氮二异庚腈(ABVN)共同用于St在甲苯中的溶液聚合中时，能够在65 °C下获得比本体聚合更高的转化率，聚合体系表现出一定的可控性，分子量随转化率增加呈现线性增长. 此外，研究并对比了不同ABVN/硫醚化合物摩尔比和聚合温度下的St自由基聚合行为.

Abstract

With inspiration from the structure of macromolecular thioether generated in the 9

-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)-9

-xanthene was obtained

via

a condensation reaction between xanthydrol and thiophenol in the presence of perchloric acid as catalyst. 9-(Methylthio)-9

-xanthene was obtained

via

the thioetherification of the chlorinated product of xanthydrol with sodium methyl mercaptide. The sulfurated intermediates were deprotonated by

-butyl lithium

and transformed into five target products

via

substitution reactions with three alkyl halides individually.

H-NMR

C-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 (

) 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

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

with a broadened PDI.

关键词

可控自由基聚合硫醚苯乙烯本体聚合溶液聚合

Keywords

Controlled radical polymerizationThioetherStyreneBulk polymerizationSolution polymerization

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