Stella Afroditi Mountaki, Richard Whitfield, Evelina Liarou, Nghia P. Truong and Athina Anastasaki*,
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引用次数: 0
摘要
虽然绝大多数受控自由基聚合都采用了耐氧策略,但由于高单体回收率通常需要较低的自由基浓度,因此耐氧溶液解聚尤其具有挑战性。这里介绍的是一种露天原子转移自由基聚合(ATRP)解聚法,通过引入少量挥发性共溶剂来彻底去除氧气。超快解聚(即 2 分钟)可在开放容器中有效进行,从而实现极高的单体回收率(即解聚效率高达 91%),与完全脱氧的类似物相当。氧探针研究与详细的解聚动力学相结合,揭示了低沸点共溶剂在反应前除去氧气的重要性,从而促进了有效的露天解聚。通过使用一系列不同的配体和在高聚合物负载量(1 M 单体重复单元浓度)下进行反应,证明了该方法的多功能性,而不会明显影响产率。这种方法为化学回收 ATRP 合成聚合物提供了一条完全耐氧、简便、高效的途径,从而实现了令人兴奋的新应用。
Open-Air Chemical Recycling: Fully Oxygen-Tolerant ATRP Depolymerization
While oxygen-tolerant strategies have been overwhelmingly developed for controlled radical polymerizations, the low radical concentrations typically required for high monomer recovery render oxygen-tolerant solution depolymerizations particularly challenging. Here, an open-air atom transfer radical polymerization (ATRP) depolymerization is presented, whereby a small amount of a volatile cosolvent is introduced as a means to thoroughly remove oxygen. Ultrafast depolymerization (i.e., 2 min) could efficiently proceed in an open vessel, allowing a very high monomer retrieval to be achieved (i.e., ∼91% depolymerization efficiency), on par with that of the fully deoxygenated analogue. Oxygen probe studies combined with detailed depolymerization kinetics revealed the importance of the low-boiling point cosolvent in removing oxygen prior to the reaction, thus facilitating effective open-air depolymerization. The versatility of the methodology was demonstrated by performing reactions with a range of different ligands and at high polymer loadings (1 M monomer repeat unit concentration) without significantly compromising the yield. This approach provides a fully oxygen-tolerant, facile, and efficient route to chemically recycle ATRP-synthesized polymers, enabling exciting new applications.
期刊介绍:
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