Sequential “Click” Approach to Polyhedral Oligomeric Silsesquioxane-Based Shape Amphiphiles
Sequential “Click” Approach to Polyhedral Oligomeric Silsesquioxane-Based Shape Amphiphiles
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DOI：
10.1021/ma3013256
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发表时间：
2012-10
期刊：
影响因子：
5.5
通讯作者：
K. Yue;Chang Liu;Kai Guo;Xinfei Yu;Mingjun Huang;Yiwen Li;C. Wesdemiotis;Stephen Z. D. Cheng
中科院分区：
文献类型：
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作者：
K. Yue;Chang Liu;Kai Guo;Xinfei Yu;Mingjun Huang;Yiwen Li;C. Wesdemiotis;Stephen Z. D. Cheng
本文报道了一种高效的、模块化的、连续的“点击”法合成基于聚合物链的多面体低聚倍半硅氧烷（POSS）的两亲分子。这种方法结合了“嫁接”和“后功能化”战略。它涉及铜催化的Huisgen [3 + 2]环加成（CuAAC）用于POSS-聚合物连接和随后的硫醇-烯加成反应用于POSS笼官能化。从容易获得的带有一个炔和七个乙烯基的POSS前体（VPOSS-炔）开始，CuAAC反应有效地确保POSS和叠氮化物官能化聚合物之间的化学计量键合，而不需要在纯化过程中进行分馏。通过合成VPOSS-PS和VPOSS-PEO，在两种具有代表性的聚合物体系，疏水性聚苯乙烯（PS）和亲水性聚（环氧乙烷）（PEO）中证明了模块化。随后应用硫醇-烯反应将POSS笼状量子点上的所有乙烯基转化为乙烯基。
This paper reports a highly efficient and modular sequential “click” approach for the syntheses of shape amphiphiles based on polymer-tethered polyhedral oligomeric silsesquioxane (POSS). This approach combines both “grafting-to” and “post-functionalization” strategies. It involves the copper-catalyzed Huisgen [3 + 2] cycloaddition (CuAAC) for POSS–polymer ligation and subsequent thiol–ene addition reaction for POSS cage functionalization. Starting from a readily available POSS precursor bearing one alkyne and seven vinyl groups (VPOSS–alkyne), the CuAAC reaction is effective in ensuring the stoichiometric bonding between POSS and azide-functionalized polymers, with no need for fractionation in the purification process. The modularity was demonstrated in two representative polymer systems, hydrophobic polystyrene (PS) and hydrophilic poly(ethylene oxide) (PEO), by the synthesis of VPOSS–PS and VPOSS–PEO. The thiol–ene reaction was subsequently applied to convert all the vinyl groups on the POSS cage quant...