A dual initiator approach for oxygen tolerant RAFT polymerization.
A dual initiator approach for oxygen tolerant RAFT polymerization.
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DOI：
10.1039/d2py00603k
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发表时间：
2022-09
影响因子：
4.6
通讯作者：
N. G. Taylor;Marcus H. Reis;Travis P Varner;Johann L. Rapp;Alexis Sarabia;Frank A. Leibfarth
中科院分区：
文献类型：
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作者：
N. G. Taylor;Marcus H. Reis;Travis P Varner;Johann L. Rapp;Alexis Sarabia;Frank A. Leibfarth
可逆失活自由基聚合是合成功能材料和杂化材料的重要方法。进行这些过程的瓶颈是需要保持无氧条件。在这里，我们报告了一个广泛适用的方法，以“通过”氧使用两个自由基引发剂具有不同的均裂率的协同组合。同时原位监测氧和单体的浓度提供了对两种引发剂的功能的了解，并能够识别有效去除溶解氧和在露天条件下控制聚合的条件。通过了解反应容器的表面积与体积比如何影响开放式聚合，使用丙烯酸酯、苯乙烯和甲基丙烯酸酯单体生产了定义明确的聚合物，这些单体各自代表了“通过”氧气聚合方法的范围的扩展。在管式反应器中使用连续流动化学的这种方法的演示提供了对反应顶部空间如何影响PTO RAFT聚合的更完整的结构-反应性理解。
Reversible-deactivation radical polymerizations are privileged approaches for the synthesis of functional and hybrid materials. A bottleneck for conducting these processes is the need to maintain oxygen free conditions. Herein we report a broadly applicable approach to "polymerize through" oxygen using the synergistic combination of two radical initiators having different rates of homolysis. The in situ monitoring of the concentrations of oxygen and monomer simultaneously provided insight into the function of the two initiators and enabled the identification of conditions to effectively remove dissolved oxygen and control polymerization under open-to-air conditions. By understanding how the surface area to volume ratio of reaction vessels influence open-to-air polymerizations, well-defined polymers were produced using acrylate, styrenic, and methacrylate monomers, which each represent an expansion of scope for the "polymerizing through" oxygen approach. Demonstration of this method in tubular reactors using continuous flow chemistry provided a more complete structure-reactivity understanding of how reaction headspace influences PTO RAFT polymerizations.