Fast and catalyst-free hetero-Diels-Alder chemistry for on demand cyclable bonding/debonding materials
Fast and catalyst-free hetero-Diels-Alder chemistry for on demand cyclable bonding/debonding materials
复制标题
DOI：
10.1039/c3py00476g
复制
发表时间：
2013-01-01
影响因子：
4.6
通讯作者：
Barner-Kowollik, Christopher
中科院分区：
文献类型：
--
作者：
Oehlenschlaeger, Kim K.;Guimard, Nathalie K.;Barner-Kowollik, Christopher
通过两步一锅法合成了一种新的含氰基Z-基团的二硫酯（氰基二硫酯（CDTE））。已经发现氰基取代的二硫酯在环境温度下进行快速可逆的杂-Diels-桤木（HDA）反应，而不需要催化剂，如ESI-MS和UV-Vis实验所证明的。为了将按需键合/脱键合系统应用于材料科学，合成了氰基-二硫代酯二连接体，并在与双环戊二烯聚合物的基于HDA的聚合反应中用作双官能亲二烯体。通过在线紫外-可见光谱、在线核磁共振光谱、在线高温DLS、GPC原位捕获实验和高水平从头算分子轨道计算，证明了聚合物体系的可逆键合。
A new dithioester possessing a cyano Z-group (cyano-dithioester (CDTE)) has been synthesized via a 2-step, one-pot reaction. The cyano-substituted dithioester has been found to undergo fast reversible hetero-Diels-Alder (HDA) reactions at ambient temperature, without the need for a catalyst, as demonstrated by ESI-MS and UV-Vis experiments. To apply the bonding/debonding on demand system to materials science, a cyano-dithioester di-linker was synthesized and employed as a di-functional dienophile in a HDA-based polymerization reaction with a bis-cyclopentadiene polymer. The reversible bonding of the polymer systems were demonstrated by on-line UV-Vis spectroscopy, on-line NMR spectroscopy, and on-line high temperature DLS, as well as via GPC in situ trapping experiments and high-level ab initio molecular orbital calculations.