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 (Đ 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 (Đs ∼ 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.

中文翻译：

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低毒溶剂中光诱导铁催化 ATRP 的可再生单体：一种更环保的方法


通过更可持续的方法从可再生资源生产聚合物变得越来越重要。在此，我们提出了从生物基可再生资源中获得的单体的聚合，在低毒性溶剂中采用环保的光诱导铁催化原子转移自由基聚合（ATRP）。我们证明，可再生单体可以成功聚合成具有受控分子量和窄摩尔​​质量分布（ Đ低至1.17）的可持续聚合物。这与可逆加成-断裂链转移 (RAFT) 聚合形成鲜明对比，后者可以说是聚合生物基单体最常用的方法，导致这些特定单体的分子量控制较差且分散度较高 ( Đ s ∼ 1.4)。通过间歇性“开/关”循环证明的时间控制、各种单体和链长的受控聚合、耐氧性以及以嵌段共聚物的合成为例的高端基团保真度，进一步凸显了我们方法的多功能性。这项工作强调了光诱导铁催化 ATRP 作为合成可再生聚合物的强大工具。