Li Jia, He Junpo
The State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Polymers and Polymer Composite Materials, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China.
ACS Macro Lett. 2015 Apr 21;4(4):372-376. doi: 10.1021/acsmacrolett.5b00125. Epub 2015 Mar 16.
We hereby report a strategy to synthesize sequence-regulated substituted polyacetylenes using living anionic polymerization of designed monomers, that is, 2,4-disubstituted butadienes. It is found that proper substituents, such as 2-isopropyl-4-phenyl, lead to nearly 100% 1,4-addition during the polymerization, thus, giving product with high regioregularity, precise molecular weight, and narrow molecular weight distribution. The product is convertible into sequence-regulated substituted polyacetylene by oxidative dehydrogenation using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Block copolymers containing polyacetylene segment are also prepared. Owing to the versatility of the anionic reactions, the present strategy can serve as a powerful tool of precise control on polymer chain microstructure, architecture, and functionalities in the same time.
我们在此报告一种使用设计单体（即2,4-二取代丁二烯）的活性阴离子聚合来合成序列规整取代聚乙炔的策略。研究发现，适当的取代基，如2-异丙基-4-苯基，会导致聚合过程中几乎100%的1,4-加成，从而得到具有高区域规整性、精确分子量和窄分子量分布的产物。该产物可通过使用2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）进行氧化脱氢转化为序列规整取代聚乙炔。还制备了含有聚乙炔链段的嵌段共聚物。由于阴离子反应的多功能性，本策略可同时作为精确控制聚合物链微观结构、结构和功能的有力工具。
