Kottisch Veronika, Jermaks Janis, Mak Joe-Yee, Woltornist Ryan A, Lambert Tristan H, Fors Brett P
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853, USA.
Angew Chem Int Ed Engl. 2021 Feb 23;60(9):4535-4539. doi: 10.1002/anie.202013419. Epub 2020 Dec 14.
The synthesis of high-molecular-weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain-transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)-organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.
在温和条件下合成高分子量的聚乙烯醚是一项重大挑战，因为阳离子聚合反应对链转移和终止事件高度敏感。我们发现了一种新型且高效的氢键供体（HBD）-有机酸对，它能够在环境条件下促进乙烯醚的可控阳离子聚合，且单体相容性极佳。在无需对试剂进行精细纯化的情况下，1小时内即可制备出摩尔质量超过50 kg/mol的聚乙烯醚。通过对HBD结构的修饰，可以调节聚合速率，而密度泛函理论（DFT）计算有助于阐明HBD、有机酸和聚合物链端之间关键的分子间相互作用。
