Yao Zhaoling, Braidy Nadi, Botton Gianluigi A, Adronov Alex
Departments of Chemistry, Materials Science and Engineering, and the Brockhouse Institute for Materials Research (BIMR), McMaster University, Hamilton, Ontario L8S 4M1, Canada.
J Am Chem Soc. 2003 Dec 24;125(51):16015-24. doi: 10.1021/ja037564y.
Single-walled carbon nanotubes were functionalized along their sidewalls with phenol groups using the 1,3-dipolar cycloaddition reaction. These phenols could be further derivatized with 2-bromoisobutyryl bromide, resulting in the attachment of atom transfer radical polymerization initiators to the sidewalls of the nanotubes. These initiators were found to be active in the polymerization of methyl methacrylate and tert-butyl acrylate from the surface of the nanotubes. However, the polymerizations were not controlled, leading to the production of high molecular weight polymers with relatively large polydispersities. The resulting polymerized nanotubes were analyzed by IR, Raman spectroscopy, DSC, TEM, and AFM. The nanotubes functionalized with poly(methyl methacrylate) were found to be insoluble, while those functionalized with poly(tert-butyl acrylate) were soluble in a variety of organic solvents. The tert-butyl groups of these appended polymers could also be removed to produce nanotubes functionalized with poly(acrylic acid), resulting in structures that are soluble in aqueous solutions.
使用1,3 - 偶极环加成反应，在单壁碳纳米管的侧壁上用酚基进行功能化修饰。这些酚类可以进一步用2 - 溴异丁酰溴衍生化，从而使原子转移自由基聚合引发剂连接到纳米管的侧壁上。发现这些引发剂在纳米管表面引发甲基丙烯酸甲酯和丙烯酸叔丁酯的聚合反应时具有活性。然而，聚合反应不受控制，导致生成具有相对较大多分散性的高分子量聚合物。通过红外光谱（IR）、拉曼光谱、差示扫描量热法（DSC）、透射电子显微镜（TEM）和原子力显微镜（AFM）对所得的聚合纳米管进行分析。发现用聚甲基丙烯酸甲酯功能化的纳米管不溶，而用聚丙烯酸叔丁酯功能化的纳米管可溶于多种有机溶剂。这些连接聚合物的叔丁基也可以被去除，以制备用聚丙烯酸功能化的纳米管，得到可溶于水溶液的结构。
