Driessen Frank, Martens Steven, Meyer Bernhard De, Du Prez Filip E, Espeel Pieter
Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4-bis, B-9000, Ghent, Belgium.
Macromol Rapid Commun. 2016 Jun;37(12):947-51. doi: 10.1002/marc.201600150. Epub 2016 May 4.
A straightforward synthetic procedure for the double modification and polymer-polymer conjugation of telechelic polymers is performed through amine-thiol-ene conjugation. Thiolactone end-functionalized polymers are prepared via two different methods, through controlled radical polymerization of a thiolactone-containing initiator, or by modification of available end-functionalized polymers. Next, these different linear polymers are treated with a variety of amine/acrylate-combinations in a one-pot procedure, creating a library of tailored end-functionalized polymers. End group conversions are monitored via SEC, NMR, and MALDI-TOF analysis, confirming the quantitative modification after each step. Finally, this strategy is applied for the synthesis of block copolymers via polymer-polymer conjugation and the successful outcome is analyzed via LCxSEC measurements.
通过胺-硫醇-烯共轭反应，实现了遥爪聚合物的双重修饰及聚合物-聚合物共轭的直接合成方法。硫内酯端基功能化聚合物可通过两种不同方法制备，一种是通过含硫内酯引发剂的可控自由基聚合，另一种是对现有的端基功能化聚合物进行修饰。接下来，将这些不同的线性聚合物在一锅法中用多种胺/丙烯酸酯组合进行处理，从而创建一系列定制的端基功能化聚合物库。通过尺寸排阻色谱（SEC）、核磁共振（NMR）和基质辅助激光解吸电离飞行时间质谱（MALDI-TOF）分析监测端基转化率，证实了每一步反应后的定量修饰。最后，将该策略应用于通过聚合物-聚合物共轭合成嵌段共聚物，并通过液相色谱-尺寸排阻色谱（LCxSEC）测量分析成功结果。
