Reversing RAFT Polymerization: Near-Quantitative Monomer Generation Via a Catalyst-Free Depolymerization Approach.
Reversing RAFT Polymerization: Near-Quantitative Monomer Generation Via a Catalyst-Free Depolymerization Approach.
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DOI：
10.1021/jacs.2c00963
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发表时间：
2022-03-16
影响因子：
15
通讯作者：
Anastasaki A
中科院分区：
文献类型：
--
作者：
Wang HS;Truong NP;Pei Z;Coote ML;Anastasaki A
逆可控自由基聚合和再生单体的能力对基础研究和应用都是非常有益的，但实现这一点仍然非常具有挑战性。在这里，我们报道了通过可逆加成-断裂链转移(RAFT)聚合制备的各种线型、大体积、交联型和功能化的聚甲基丙烯酸酯的近定量(高达92%)和无催化剂的解聚。我们方法的关键是利用RAFT聚合物的高端基团保真度来产生120°C的链端自由基。这些自由基会引发常规聚合物(例如聚甲基丙烯酸甲酯)和大体积聚合物(例如聚乙二醇甲醚甲基丙烯酸酯)的快速解压。重要的是，解聚产物可用于重建线性聚合物或创建一种全新的也可解聚的不溶性凝胶。这项工作扩展了由可控自由基聚合制备的聚合物的潜力，突破了解聚的界限，提供了有趣的机理方面，并使新的应用成为可能。
The ability to reverse controlled radical polymerization and regenerate the monomer would be highly beneficial for both fundamental research and applications, yet this has remained very challenging to achieve. Herein, we report a near-quantitative (up to 92%) and catalyst-free depolymerization of various linear, bulky, cross-linked, and functional polymethacrylates made by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Key to our approach is to exploit the high end-group fidelity of RAFT polymers to generate chain-end radicals at 120 °C. These radicals trigger a rapid unzipping of both conventional (e.g., poly(methyl methacrylate)) and bulky (e.g., poly(oligo(ethylene glycol) methyl ether methacrylate)) polymers. Importantly, the depolymerization product can be utilized to either reconstruct the linear polymer or create an entirely new insoluble gel that can also be subjected to depolymerization. This work expands the potential of polymers made by controlled radical polymerization, pushes the boundaries of depolymerization, offers intriguing mechanistic aspects, and enables new applications.
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影响因子：
5.5
作者：
Bates, Christopher M.;Maher, Michael J.;Willson, C. Grant
通讯作者：
Willson, C. Grant
影响因子：
5.9
作者：
Bekanova, Marianna Z.;Neumolotov, Nikolay K.;Kudryavtsev, Yaroslav V.
通讯作者：
Kudryavtsev, Yaroslav V.
影响因子：
--
作者：
DAINTON, FS;IVIN, KJ
通讯作者：
IVIN, KJ
影响因子：
6
作者：
KAMINSKY, W;FRANCK, J
通讯作者：
FRANCK, J
DOI：
10.1002/pol.1980.170180715
发表时间：
1980-01-01
影响因子：
--
作者：
OTSU, T;YAMADA, B;MORI, S
通讯作者：
MORI, S