Low-Dispersity Polymers via Free Radical Alternating Copolymerization: Effects of Charge-Transfer-Complexes

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Angewandte Chemie International Edition Pub Date : 2024-07-26 DOI:10.1002/anie.202409744
Yu Gu, Zexi Zhang, Tianyi Gao, Prof. Dr. Rafael Gómez-Bombarelli, Prof. Dr. Mao Chen
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Abstract

Alternating copolymers are crucial for diverse applications. While dispersity (Ð, also known as molecular weight distribution, MWD) influences the properties of polymers, achieving low dispersities in alternating copolymers poses a notable challenge via free radical polymerizations (FRPs). In this work, we demonstrated an unexpected discovery that dispersities are affected by the participation of charge transfer complexes (CTCs) formed between monomer pairs during free radical alternating copolymerization, which have inspired the successful synthesis of various alternating copolymers with low dispersities (>30 examples, Ð=1.13–1.39) under visible-light irradiation. The synthetic method is compatible with binary, ternary and quaternary alternating copolymerizations and is expandable for both fluorinated and non-fluorinated monomer pairs. DFT calculations combined with model experiments indicated that CTC-absent reaction exhibits higher propagation rates and affords fewer radical terminations, which could contribute to low dispersities. Based on the integration of Monte Carlo simulation and Bayesian optimization, we established the relationship map between FRP parameter space and dispersity, further suggested the correlation between low dispersities and higher propagation rates. Our research sheds light on dispersity control via FRPs and creates a novel platform to investigate polymer dispersity through machine learning.

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通过自由基交替共聚产生低分散性聚合物:电荷转移络合物的影响。
交替共聚物对各种应用至关重要。虽然分散性(Ɖ,又称分子量分布,MWD)会影响聚合物的特性,但通过自由基聚合(FRPs)实现交替共聚物的低分散性却是一个显著的挑战。在这项工作中,我们意外地发现,在自由基交替共聚过程中,单体对之间形成的电荷转移复合物(CTCs)的参与会影响分散性,这启发我们在可见光照射下成功合成了各种低分散性(大于 30 例,Ɖ = 1.13-1.39)的交替共聚物。该合成方法适用于二元、三元和四元交替共聚物,并可扩展至含氟和不含氟的单体对。DFT 计算与模型实验相结合表明,不含四氯化碳的反应具有更高的传播速度,并能产生更少的自由基终止,这可能是造成低分散性的原因之一。在蒙特卡罗模拟和贝叶斯优化相结合的基础上,我们建立了 FRP 参数空间与分散性之间的关系图,进一步提出了低分散性与高传播速率之间的相关性。我们的研究揭示了 FRP 的分散性控制,并创建了一个通过机器学习研究聚合物分散性的新平台。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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