Controlled Cationic Polymerization: Single-Component Initiation under Ambient Conditions
Controlled Cationic Polymerization: Single-Component Initiation under Ambient Conditions
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DOI：
10.1021/jacs.9b04961
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发表时间：
2019-07-10
影响因子：
15
通讯作者：
Fors, Brett P.
中科院分区：
文献类型：
--
作者：
Kottisch, Veronika;O'Leary, Jacob;Fors, Brett P.
阳离子聚合为制备具有优异控制的大分子提供了有价值的策略，但其固有地对杂质敏感，并且通常需要严格的试剂纯化、低温和严格无水的反应条件。通过使用五碳甲氧基环戊二烯（PCCP）作为单组分引发有机酸，我们发现，不同的图书馆的乙烯基醚可以在环境条件下可控聚合。此外，即使没有严格的单体纯化，也能保持优异的链端保真度。我们假设，紧密的离子复合物之间的PCCP阴离子和oxocarbenium离子链端防止链转移事件，并使聚合与生活的特点。此外，用官能亲核试剂终止聚合允许以高产率进行链端官能化。
Cationic polymerizations provide a valuable strategy for preparing macromolecules with excellent control but are inherently sensitive to impurities and commonly require rigorous reagent purification, low temperatures, and strictly anhydrous reaction conditions. By using pentacarbomethoxycyclopentadiene (PCCP) as the single-component initiating organic acid, we found that a diverse library of vinyl ethers can be controllably polymerized under ambient conditions. Additionally, excellent chain-end fidelity is maintained even without rigorous monomer purification. We hypothesize that a tight ion complex between the PCCP anion and the oxocarbenium ion chain end prevents chain-transfer events and enables a polymerization with living characteristics. Furthermore, terminating the polymerization with functional nucleophiles allows for chain-end functionalization in high yields.