Song Bo, Zhang Rongyuan, Hu Rong, Chen Xu, Liu Dongming, Guo Jiali, Xu Xiaotian, Qin Anjun, Tang Ben Zhong
State Key Laboratory of Luminescent Materials and Devices Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates Center for Aggregation-Induced Emission South China University of Technology Guangzhou 510640 China.
Department of Urology The First Affiliated Hospital of Soochow University 188 Shizi RD Suzhou 215006 China.
Adv Sci (Weinh). 2020 Jul 8;7(17):2000465. doi: 10.1002/advs.202000465. eCollection 2020 Sep.
Hyperbranched polymers constructed from CO possess unique architectures and properties; however, they are difficult to prepare. In this work, CO-based, hyperbranched poly(alkynoate)s (hb-PAs) with high molecular weights and degrees of branching are facilely prepared under atmospheric pressure in only 3 h. Because hb-PAs possess two types of ethynyl groups with different reactivities, they can undergo site-selective, three-step functionalizations with nearly 100% conversion in each step. Taking advantage of this unique feature, functional hb-PAs with versatile properties are constructed that could be selectively tailored to contain hydrophilic oligo(ethylene glycol) chains in their branched chains, on their periphery, or both via tandem polymerizations. Hyperbranched polyprodrug amphiphiles with high drug loading content (44.3 wt%) are also generated, along with an artificial light-harvesting system with high energy transfer efficiency (up to 92%) and white-light-emitting polymers. This work not only provides an efficient pathway to convert CO into hyperbranched polymers, but also offers an effective platform for site-selective multistep functionalizations toward functional polymeric materials.
由一氧化碳构建的超支化聚合物具有独特的结构和性能；然而，它们难以制备。在这项工作中，在大气压下仅需3小时就能轻松制备出具有高分子量和支化度的基于一氧化碳的超支化聚（炔酸酯）（hb-PAs）。由于hb-PAs具有两种反应活性不同的乙炔基，它们可以进行位点选择性的三步官能化反应，每一步的转化率接近100%。利用这一独特特性，构建了具有多种性能的功能性hb-PAs，通过串联聚合反应可以选择性地在其支链、外围或两者中包含亲水性聚乙二醇链。还制备出了具有高载药量（44.3 wt%）的超支化聚前药两亲物，以及具有高能量转移效率（高达92%）的人工光捕获系统和白色发光聚合物。这项工作不仅提供了一条将一氧化碳转化为超支化聚合物的有效途径，还为功能性聚合物材料的位点选择性多步官能化提供了一个有效的平台。
