Stereoregular Two-Dimensional Polymers Constructed by Topochemical Polymerization,Macromolecules

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Stereoregular Two-Dimensional Polymers Constructed by Topochemical Polymerization
Macromolecules ( IF 5.1 ) Pub Date : 2015-04-30 00:00:00 , DOI: 10.1021/acs.macromol.5b00109
Zhihan Wang ₁ , Katelyn Randazzo ₁ , Xiaodong Hou ₁ , Jeffrey Simpson ₂ , Jochem Struppe ₃ , Angel Ugrinov ₄ , Brent Kastern ₁ , Erin Wysocki ₁ , Qianli R. Chu ₁

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Two stereoregular 2D polyesters were synthesized by using topochemical polymerization of symmetric four-armed monomers. The monomers contain reactive carbon–carbon double bond(s) on each arm. The critical assemblies with multiple preorganized reactive centers were characterized by powder and single crystal X-ray diffraction. The solvent-free polymerization could be carried out with sunlight or UV irradiation. The locally confined photopolymerization process dimerized all of the olefins within the 2D bricklayer packing, which led to the formation of 2D polymers in the solid state. The process was monitored by FT-IR, and the products were confirmed by solid state NMR. After hydrolysis of the 2D polyester, the newly formed carbon–carbon single bonds during the [2 + 2] photocyclization were directly revealed by the single crystal structure of the hydrolysis product. Ultrathin sheets of the 2D polymer were observed under SEM and TEM after exfoliation.

中文翻译：

拓扑化学聚合构建立体球形二维聚合物

通过对称四臂单体的拓扑化学聚合反应，合成了两种立构规整的2D聚酯。单体在每个臂上均包含反应性碳-碳双键。具有多个预组织的反应中心的临界组件通过粉末和单晶X射线衍射表征。可以在阳光或紫外线照射下进行无溶剂聚合。局部受限的光聚合过程使2D瓦工填料中的所有烯烃二聚，这导致形成固态的2D聚合物。通过FT-IR监测该过程，并通过固态NMR确认产物。2D聚酯水解后，水解产物的单晶结构直接揭示了[2 + 2]光环化过程中新形成的碳-碳单键。剥离后，在SEM和TEM下观察到二维聚合物的超薄片。

更新日期：2015-04-30

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