Cationic ring-opening polymerization of cyclic monothiocarbonates : Varying the polymer main chain by neighboring group participation
Cationic ring-opening polymerization of cyclic monothiocarbonates : Varying the polymer main chain by neighboring group participation
复制标题
环状单硫代碳酸酯的阳离子开环聚合：通过邻近基团的参与改变聚合物主链
DOI：
10.1021/ma010653f
复制
发表时间：
2001
期刊：
影响因子：
5.5
通讯作者：
T. Endo
中科院分区：
文献类型：
--
作者：
N. Nemoto;Xiaoyu Xu;F. Sanda;T. Endo
在2，3-二甲基-1-苯基-3-吡唑啉-5-酮（安替比林）存在下，由相应的二醇与硫光气反应，合成了新型五元环状单硫代碳酸酯衍生物4-苯甲酰氧基甲基-1，3-二氧戊环-2-酮（TC 1）和4-苯甲酰氧基甲基-1，3-二氧戊环-2-酮（TC 2）。采用几种阳离子引发剂对TC 1和TC 2进行阳离子开环聚合，得到了在普通有机溶剂中溶解性良好的聚硫代碳酸酯，并伴有硫代碳酸酯基团的异构化。TC 1的聚合反应涉及酯基邻近基团的参与。从TC 1和TC 2获得的聚合物的主链是不同的。主链结构取决于硫代碳酸酯环上的取代基，即，是否涉及相邻酯基的参与。
Novel five-membered cyclic monothiocarbonate derivatives, 4-benzoyloxymethyl-1,3-dioxolane-2-thione (TC1) and 4-phenoxymethyl-1,3-dioxolane-2-thione (TC2), were synthesized by reaction of the corresponding diols and thiophosgene in the presence of 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (antipyrine) in chloroform. The cationic ring-opening polymerization of TC1 and TC2 using several cationic initiators afforded polythiocarbonate with good solubility in common organic solvents accompanying isomerization of thiocarbonate group. The polymerization of TC1 proceeded involving the neighboring group participation of the ester group. The main chains of the polymers obtained from TC1 and TC2 were different. The main chain structure depends on the substituent on the thiocarbonate ring, i.e., whether neighboring ester group participation was involved or not.