Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes
Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes
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7,7,8,8-四(芳氧基羰基)-对醌二甲烷热固相聚合中立构聚合物束状组装体的形成
DOI：
10.1021/acs.macromol.6b00349
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发表时间：
2016
期刊：
影响因子：
5.5
通讯作者：
Mikiji Miyata
中科院分区：
文献类型：
--
作者：
Takahito Itoh;Erica Morita;Ryouhei Takakura;Hiroto Nakajima;Takahiro Uno;Masataka Kubo;Norimitsu Tohnai;Mikiji Miyata
合成了含有大量芳氧基的7,7,8,8-四（芳氧羰基）-对喹啉二甲烷，如苯氧基（1a）、五氟双酶氧基（1b）以及苯氧基和五氟双酶氧基（1c）。我们以1a - 1c的晶体结构为基础，研究了这些庞大基团对固态热聚合反应的影响。热聚合得到1,6-反式正规整聚合物，在110°C条件下1a、150°C条件下1b和110°C条件下1c分别需要1天、1天和6天。它们最初的晶体形状在聚合过程中保留在外观上，以产生它们的聚合链的固体束组装。x射线单晶结构分析表明，它们的晶体采用适合一维聚合的分子排列，并沿一个结晶轴加成1,6-反式加成。这种排列导致了1波段的膨胀聚合1波段的收缩1波段。与传统的拓扑化学聚合制备的聚合物相比，所得到的立体规则聚合物形成的束束组装不那么有序。通过这种方式，庞大的芳氧基使我们能够观察到分子组装模式与聚合行为之间的密切关系，为证明热固态聚合的多样性提供了第一个例子。
7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes with bulky aryloxy groups such as benzyloxy (1a), pentafluorobenzyloxy (1b), and both benzyloxy and pentafluorobenzyloxy (1c) were synthesized. We investigated effects of these bulky groups on thermal solid-state polymerization reactivities on the basis of crystal structures of1a–1c. Thermal polymerizations gave 1,6-trans-type stereoregular polymers in quantitative yields in 1 day at 110 °C for1a, 1 day at 150 °C for1b, and 6 days at 110 °C for1c. Their initial crystal shapes were retained in appearance during polymerization to yield solid bundle assemblies of their polymeric chains. X-ray single-crystal structure analysis indicates that their crystals adopt molecular arrangements suitable for one-dimensional polymerization with the 1,6-trans-type addition along one crystallographic axis. Such arrangements led to expansion polymerization of1band contraction one of1c. The resulting stereoregular polymers form less ordered bundle assemblies than those prepared by the conventional topochemical polymerization. In this manner, the bulky aryloxy groups enabled us to observe a close relation between the molecular assembly modes and the polymerization behaviors, providing the first example for proving diversity of thermal solid-state polymerizations.