-Laboratory of Polymeric Materials, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, Zurich 8093, Switzerland.
ACS Macro Lett. 2022 Jul 19;11(7):841-846. doi: 10.1021/acsmacrolett.2c00302. Epub 2022 Jun 22.
Producing polymers from renewable resources via more sustainable approaches has become increasingly important. Herein we present the polymerization of monomers obtained from biobased renewable resources, employing an environmentally friendly photoinduced iron-catalyzed atom transfer radical polymerization (ATRP) in low-toxicity solvents. We demonstrate that renewable monomers can be successfully polymerized into sustainable polymers with controlled molecular weights and narrow molar mass distributions ( as low as 1.17). This is in contrast to reversible addition-fragmentation chain-transfer (RAFT) polymerization, arguably the most commonly employed method to polymerize biobased monomers, which led to poorer molecular weight control and higher dispersities for these specific monomers (s ∼ 1.4). The versatility of our approach was further highlighted by the temporal control demonstrated through intermittent "on/off" cycles, controlled polymerizations of a variety of monomers and chain lengths, oxygen-tolerance, and high end-group fidelity exemplified by the synthesis of block copolymers. This work highlights photoinduced iron-catalyzed ATRP as a powerful tool for the synthesis of renewable polymers.
通过更可持续的方法从可再生资源中生产聚合物变得越来越重要。在此，我们展示了在低毒性溶剂中使用环保的光诱导铁催化原子转移自由基聚合（ATRP）聚合从生物基可再生资源获得的单体。我们证明可再生单体可以成功聚合为具有可控分子量和较窄分子量分布的可持续聚合物（低至 1.17）。这与可逆加成-断裂链转移（RAFT）聚合形成对比，RAFT 聚合是聚合生物基单体最常用的方法，但对于这些特定单体，其分子量控制和多分散性较差（s ∼ 1.4）。通过间歇“开/关”循环、各种单体和链长的可控聚合、耐氧性以及通过合成嵌段共聚物示例证明的高端基保真度，进一步突出了我们方法的多功能性。这项工作强调了光诱导铁催化 ATRP 是合成可再生聚合物的有力工具。
