Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan.
J Am Chem Soc. 2023 May 24;145(20):10948-10953. doi: 10.1021/jacs.3c01796. Epub 2023 Apr 20.
Direct radical addition reactions of thiocarbonyl (C═S) groups unaccompanied by β-scission have rarely been reported despite their potential for constructing various sulfur-containing compounds. Herein, we report direct radical copolymerizations of the C═S double bonds of simple thioamide derivatives and the C═C double bonds of common vinyl monomers to produce novel degradable vinyl polymers that contain thioether units in the backbones. In particular, N-acylated thioformamides copolymerized smoothly with various vinyl monomers, such as methyl acrylate, vinyl acetate, ,-dimethylacrylamide, and styrene. RAFT copolymerization was also successfully mediated. The resultant copolymers had high glass transition temperatures and were readily degradable under ambient conditions. This work will expand the potential for use of thiocarbonyl compounds in radical reactions and develop novel poly(thioether)-vinyl polymer hybrid materials with unusual properties.
尽管硫羰基（C=S）基团的直接自由基加成反应伴随着β-断裂的发生很少有报道，但它们在构建各种含硫化合物方面具有潜在的应用价值。在此，我们报道了简单硫代酰胺衍生物的 C=S 双键与常见的乙烯基单体的 C=C 双键的直接自由基共聚，生成含有硫醚单元的新型可降解乙烯基聚合物。特别是，N-酰化硫代甲酰胺与各种乙烯基单体如甲基丙烯酸酯、醋酸乙烯酯、-二甲基丙烯酰胺和苯乙烯共聚非常顺利。RAFT 共聚也得到了成功的介导。所得共聚物具有较高的玻璃化转变温度，并在环境条件下容易降解。这项工作将扩大硫羰基化合物在自由基反应中的应用潜力，并开发具有独特性质的新型聚（硫醚）-乙烯基聚合物杂化材料。
