Higashihara Tomoya, Ito Shotaro, Fukuta Seijiro, Miyane Satoshi, Ochiai Yuto, Ishizone Takashi, Ueda Mitsuru, Hirao Akira
Department of Organic Device Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan.
Division of Soft Material Chemistry, Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-13, 2-12-1, Ohokayama, Meguro-ku, Tokyo 152-8552, Japan.
ACS Macro Lett. 2016 May 17;5(5):631-635. doi: 10.1021/acsmacrolett.6b00207. Epub 2016 May 4.
The new series of ABC-type miktoarm star polymer (, A = polyisoprene (PI), B = polystyrene (PS), and C = poly(3-hexylthiophene) (P3HT)) and ABCD-type miktoarm star polymer (, A = PI, B = PS, C = poly(α-methylstyrene) (PαMS), and D = P3HT) could be synthesized by the combination of the controlled KCTP, anionic linking reaction, and Click chemistry. By the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition click reaction of the azido-chain-end-functional P3HT () with the alkyne-in-chain-functional AB diblock copolymer (A = PI and B = PS) () or alkyne-core-functional ABC miktoarm star polymer (A = PI, B = PS, and C = PαMS) (), the target and , respectively, were obtained, as confirmed by size exclusion chromatography (SEC) and proton nuclear magnetic resonance (H NMR). The thermal and optical properties of these star polymers were examined by thermal gravimetric analysis (TGA) and UV-vis spectroscopy. The dynamic scattering calorimetry (DSC), atomic force micrograph (AFM) image, and grazing incidence small-angle X-ray scattering (GISAXS) results showed that the periodic P3HT fibril nanostructures rather than microphase separation occurred in the film. In addition, it was found that highly crystalline P3HT domains aligned in the "edge-on" orientation, as supported by grazing incidence wide-angle X-ray scattering (GIWAXS).
通过可控的KCTP、阴离子连接反应和点击化学相结合，可以合成新系列的ABC型米克托臂星形聚合物（其中，A = 聚异戊二烯（PI），B = 聚苯乙烯（PS），C = 聚（3 - 己基噻吩）（P3HT））和ABCD型米克托臂星形聚合物（其中，A = PI，B = PS，C = 聚（α - 甲基苯乙烯）（PαMS），D = P3HT）。通过叠氮链端官能化的P3HT（）与链内炔基官能化的AB二嵌段共聚物（A = PI且B = PS）（）或炔基核官能化的ABC米克托臂星形聚合物（A = PI，B = PS，且C = PαMS）（）的铜（I）催化的惠斯根1,3 - 偶极环加成点击反应，分别得到了目标产物和，这通过尺寸排阻色谱法（SEC）和质子核磁共振（H NMR）得到了证实。通过热重分析（TGA）和紫外 - 可见光谱对这些星形聚合物的热性能和光学性能进行了研究。动态散射量热法（DSC）、原子力显微镜（AFM）图像和掠入射小角X射线散射（GISAXS）结果表明，在薄膜中出现的是周期性的P3HT原纤维纳米结构而非微相分离。此外，如掠入射广角X射线散射（GIWAXS）所支持的，发现高度结晶的P3HT域以“边对边”取向排列。
