Metal-Free Alkyne Polyhydrothiolation: Synthesis of Functional Poly(vinylenesulfide)s with High Stereoregularity by Regioselective Thioclick Polymerization
Metal-Free Alkyne Polyhydrothiolation: Synthesis of Functional Poly(vinylenesulfide)s with High Stereoregularity by Regioselective Thioclick Polymerization
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无金属炔烃聚氢硫醇化：通过区域选择性硫代点击聚合合成具有高立构规整性的功能性聚(亚乙烯基硫醚)
DOI：
10.1002/adfm.200901943
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发表时间：
2010-04-23
影响因子：
19
通讯作者：
Tang, Ben Zhong
中科院分区：
文献类型：
--
作者：
Jim, Cathy K. W.;Qin, Anjun;Tang, Ben Zhong
开发了一条合成富硫聚合物的新路线。4，4 '-硫代二苯乙烷（1）和亚芳基二丙酸酯（2-5）在胺的作用下的炔多氢硫醇化反应在室温下以区域选择性方式进行，家具唯一的反马尔可夫尼科夫产品的聚乙烯基硫醚（P1/2-P1/5），分子量可达32300，立体异构度高，Z含量可达81.4%，产率可达98.2%。聚合物P1/2-P1/4可溶于普通有机溶剂。它们是光学透明的，几乎所有的可见光和红外光都可以透过。由于高硫含量的聚合物，它们的膜显示高折射率（n = 1.73-1.70），在波长范围为500 - 1700 nm，以及高阿贝数（nu（D）'高达539）和低的光色散（D'低至0.002）在重要的电信波长。它们的荧光活性可通过金属络合作用进一步增强（n可达2.06），它们的膜可通过紫外光照射交联，这使得荧光染料的制备变得容易。
A new synthetic route to sulfur-rich polymers has been developed. The alkyne polyhydrothiolations of 4,4'-thiodibenzenethiol (1) and arylene dipropiolates (2-5) mediated by amines proceed at room temperature in a regioselective fashion, furnishing sole anti-Markovnikov products of poly(vinylenesulfide)s (P1/2-P1/5) with high molecular weights (M-w up to 32 300) and high stereoregularities (Z content up to 81.4%) in high yields (up to 98.2%). Polymers P1/2-P1/4 are soluble in common organic solvents. They are optically transparent, allowing almost all visible and IR light to transmit through. Thanks to the high sulfur contents of the polymers, their films show high refractive indices (n = 1.73-1.70) in the wavelength region of 500 1700 nm as well as high Abbe numbers (nu(D)' up to 539) and low optical dispersions (D' down to 0.002) at wavelengths important for telecommunications. Their refractivities can be further enhanced (n up to 2.06) by metal complexation and their films can be crosslinked by UV irradiation, which enables ready fabrication of fluorescent photopatterns.