Zhao Yuan, Wu Haibo, Zhang Yuanyi, Wang Xing, Yang Bin, Zhang Qingdong, Ren Xu, Fu Changkui, Wei Yen, Wang Zhiming, Wang Yurong, Tao Lei
The Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu 213164, P. R. China.
ACS Macro Lett. 2015 Aug 18;4(8):843-847. doi: 10.1021/acsmacrolett.5b00428. Epub 2015 Jul 27.
A highly reactive thiourea-contained polycondensate, poly(dihydropyrimidin-2(1)-thione) (poly(DHPMT)) has been facilely synthesized via the Biginelli polycondensation using thiourea and a difunctional compound containing benzaldehyde and β-keto ester groups as monomers. The thiourea moiety in the polymer structure has similar reactivity as the thiourea, thus the poly(DHPMT) is an excellent polymer precusor for preparing new functional polymers through the postpolymerization modification (PPM) strategy. After simple reaction with functional haloalkanes, the parent poly(DHPMT) could be almost completely converted (>99%) to daughter polymers containing alkene or alkyne side groups. Then, the daughter polymers have been further transferred to granddaughter polymers through another PPM via thiol-ene or Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Besides, when 3-phenylpropargyl chloride was used as the reactant, a bright yellow fluorescent polymer could be simply achieved due to the in situ formed conjugated heterocycle in the polymer structure, further demonstrating the diversity of the functional polymers through PPM. Considering the easily available monomers, simple polycondensation, and the excellent reactivity of the thiourea moiety in the polymer structure, this thiourea-contained Biginilli polycondensate might be a versatile platform for new functional polymer preparation.
一种高反应性的含硫脲缩聚物，聚（二氢嘧啶-2(1)-硫酮）（聚（DHPMT））已通过Biginelli缩聚反应，以硫脲和一种含有苯甲醛和β-酮酯基团的双官能化合物作为单体，简便地合成出来。聚合物结构中的硫脲部分具有与硫脲相似的反应活性，因此聚（DHPMT）是通过后聚合改性（PPM）策略制备新型功能聚合物的优良聚合物前体。与功能性卤代烷简单反应后，母体聚（DHPMT）几乎可以完全（>99%）转化为含有烯烃或炔烃侧基的子聚合物。然后，通过硫醇-烯或铜（I）催化的叠氮化物-炔烃环加成（CuAAC）反应，经另一种PPM将子聚合物进一步转化为孙聚合物。此外，当使用3-苯基丙炔基氯作为反应物时，由于聚合物结构中原位形成的共轭杂环，可以简便地得到一种亮黄色荧光聚合物，进一步证明了通过PPM制备的功能聚合物的多样性。考虑到单体易于获得、缩聚反应简单以及聚合物结构中硫脲部分具有优异的反应活性，这种含硫脲的Biginelli缩聚物可能是制备新型功能聚合物的通用平台。
