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黄原酸酯负载的光引发转移终止剂(XPI)-可逆加成-断裂链转移(RAFT)聚合:便捷快速地合成复杂大分子。

Xanthate-supported photo-iniferter (XPI)-RAFT polymerization: facile and rapid access to complex macromolecules.

作者信息

Lehnen Anne-Catherine, Gurke Johannes, Bapolisi Alain M, Reifarth Martin, Bekir Marek, Hartlieb Matthias

机构信息

University of Potsdam, Institute of Chemistry Karl-Liebknecht-Straße 24-25 D-14476 Potsdam Germany

Fraunhofer Institute for Applied Polymer Research (IAP) Geiselbergstraße 69 D-14476 Potsdam Germany.

出版信息

Chem Sci. 2022 Nov 29;14(3):593-603. doi: 10.1039/d2sc05197d. eCollection 2023 Jan 18.

Abstract

Xanthate-supported photo-iniferter (XPI)-reversible addition-fragmentation chain-transfer (RAFT) polymerization is introduced as a fast and versatile photo-polymerization strategy. Small amounts of xanthate are added to conventional RAFT polymerizations to act as a photo-iniferter under light irradiation. Radical exchange is facilitated by the main CTA ensuring control over the molecular weight distribution, while xanthate enables an efficient photo-(re)activation. The photo-active moiety is thus introduced into the polymer as an end group, which makes chain extension of the produced polymers possible directly by irradiation. This is in sharp contrast to conventional photo-initiators, or photo electron transfer (PET)-RAFT polymerizations, where radical generation depends on the added small molecules. In contrast to regular photo-iniferter-RAFT polymerization, photo-activation is decoupled from polymerization control, rendering XPI-RAFT an elegant tool for the fabrication of defined and complex macromolecules. The method is oxygen tolerant and robust and was used to perform screenings in a well-plate format, and it was even possible to produce multiblock copolymers in a coffee mug under open-to-air conditions. XPI-RAFT does not rely on highly specialized equipment and qualifies as a universal tool for the straightforward synthesis of complex macromolecules. The method is user-friendly and broadens the scope of what can be achieved with photo-polymerization techniques.

摘要

黄原酸酯负载的光引发转移终止剂(XPI)-可逆加成-断裂链转移(RAFT)聚合被引入作为一种快速且通用的光聚合策略。在传统的RAFT聚合中加入少量黄原酸酯,使其在光照下充当光引发转移终止剂。主链转移剂(CTA)促进自由基交换,确保对分子量分布的控制,而黄原酸酯则能实现高效的光(再)活化。光活性部分因此作为端基引入聚合物中,这使得通过辐照直接对所制备的聚合物进行链延伸成为可能。这与传统的光引发剂或光电子转移(PET)-RAFT聚合形成鲜明对比,在传统方法中自由基的产生依赖于添加的小分子。与常规的光引发转移终止剂-RAFT聚合不同,光活化与聚合控制解耦,使XPI-RAFT成为制备特定和复杂大分子的理想工具。该方法耐氧且稳健,可用于微孔板形式的筛选,甚至在露天条件下的咖啡杯中也能制备多嵌段共聚物。XPI-RAFT不依赖于高度专业化的设备,是直接合成复杂大分子的通用工具。该方法用户友好,拓宽了光聚合技术所能实现的范围。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9bc7/9847670/eb859379430a/d2sc05197d-s1.jpg

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