Development of a transition metal-free polymerization route to functional conjugated polydiynes from a haloalkyne-based organic reaction
Development of a transition metal-free polymerization route to functional conjugated polydiynes from a haloalkyne-based organic reaction
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DOI：
10.1039/c6py00050a
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发表时间：
2016-03
影响因子：
4.6
通讯作者：
Y. Zhang;Engui Zhao;Haiqin Deng;J. Lam;B. Tang
中科院分区：
文献类型：
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作者：
Y. Zhang;Engui Zhao;Haiqin Deng;J. Lam;B. Tang
无过渡金属聚合由于其合成成本低、金属残留少、材料性能高而成为聚合物科学的研究热点。在这项工作中，我们报告了一个新的方法，这样的基础上1-卤代炔的有机反应的共轭聚二炔。在碘化钾存在下，1，2-双[4-（2-甲基苯基）-1-甲基-2-苯基]-2-甲基苯甲酰胺的聚合（碘乙炔基）苯基]-1，2-二苯基乙烯（1），1，4-双（2-碘乙炔基）苯（2）和4，4 ′-双（2-碘乙炔基）-1，1 ′-联苯（3）在N，N-二甲基甲酰胺中于120 ℃、氮气下顺利进行，生成由交替芳族和1，3-二炔部分以中等至令人满意的产率。P1在常见有机溶剂中具有良好的溶解性，而P2和P3由于其刚性结构而不溶。所有的聚合物都是热稳定的，在高达352 °C的高温下会损失5%的重量。通过旋涂P1的溶液可以容易地获得P1的均匀膜，其在宽波长范围（400-900 nm）内显示出高的且UV可调谐的折射率（n = 2.1125-1.7747）。通过铜掩模对聚合物膜进行UV照射，可以产生轮廓分明的荧光图案。因此，这项工作开辟了一个新的途径，构建共轭聚合物与先进的功能。
The development of an efficient transition metal-free polymerization route has been an active research topic in polymer science owing to its low synthetic cost and decreased metal residue and hence elevated material performance in the products. In this work, we report a new such method for constructing conjugated polydiynes based on the organic reaction of 1-haloalkyne. In the presence of potassium iodide, the polymerizations of 1,2-bis[4-(iodoethynyl)phenyl]-1,2-diphenylethene (1), 1,4-bis(2-iodoethynyl)benzene (2) and 4,4′-bis(2-iodoethynyl)-1,1′-biphenyl (3) proceed smoothly in N,N-dimethylformamide at 120 °C under nitrogen, producing P1–3 consisting of alternate aromatic and 1,3-diyne moieties in moderate to satisfactory yields. While P1 possesses good solubility in common organic solvents, P2 and P3 are insoluble due to their rigid structures. All the polymers are thermally stable, losing 5% of their weight at a high temperature of up to 352 °C. A homogeneous film of P1 can be readily obtained by spin-coating its solution, which shows high and UV-tunable refractive index (n = 2.1125–1.7747) in a wide wavelength range (400–900 nm). A well-defined fluorescent photopattern can be generated by UV irradiation of the polymer film through a copper mask. This work thus opens a new avenue for constructing conjugated polymers with advanced functionalities.