Enzyme-Deoxygenated Low Parts per Million Atom Transfer Radical Polymerization in Miniemulsion and Ab Initio Emulsion.
Enzyme-Deoxygenated Low Parts per Million Atom Transfer Radical Polymerization in Miniemulsion and Ab Initio Emulsion.
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DOI：
10.1021/acsmacrolett.8b00711
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发表时间：
2018-10
影响因子：
5.8
通讯作者：
Yi Wang;Liye Fu;K. Matyjaszewski
中科院分区：
文献类型：
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作者：
Yi Wang;Liye Fu;K. Matyjaszewski
开发耐氧可逆失活自由基聚合（RDRP）体系可以大大简化聚合物的合成，而无需多余的脱氧过程。在此，我们扩大了耐氧RDRP的应用从均匀的水溶液和有机溶液分散介质。在细乳液和从头算乳液体系中，使用不同的催化剂再生方法：ARGET、ICAR、photo和eATRP，进行葡萄糖氧化酶（GOx）脱气原子转移自由基聚合（ATRP）。所有这些聚合程序导致具有预定分子量、低分散性和高链端官能度的聚合物。用保存的对照品在较大规模上进行乳剂ATRP也是成功的。圆二色谱（CD）研究表明，阴离子表面活性剂，十二烷基硫酸钠（SDS），没有破坏的二级结构的GOx。这证实了GOx系统对于各种低ppm ATRP方法的通用性。首次报道了GOx辅助的疏水聚合物合成中的除氧。脱氧试剂的低成本和放大该过程的能力表明了工业生产的潜力，特别是对于乳液聚合。
The development of robust oxygen-tolerant reversible deactivation radical polymerization (RDRP) systems can dramatically simplify synthesis of well-defined polymers without redundant deoxygenation procedures. Herein, we broaden the application of oxygen-tolerant RDRP from homogeneous aqueous and organic solutions to dispersed media. The glucose oxidase (GOx) degassed atom transfer radical polymerization (ATRP) was conducted in miniemulsion and ab initio emulsion systems using various catalyst regeneration methods: ARGET, ICAR, photo, and eATRP. All of these polymerization procedures led to polymers with predetermined molecular weight, low dispersity, and high chain-end functionality. Emulsion ATRP on a larger scale with preserved control was also successful. Circular dichroism (CD) studies demonstrated that the anionic surfactant, sodium dodecyl sulfate (SDS), did not damage the secondary structure of GOx. This confirms the versatility of the GOx system for various low ppm ATRP methods. GOx-assisted oxygen removal in the synthesis of hydrophobic polymers is reported for the first time. The low cost of deoxygenation reagents and the ability to scale up the procedure suggest the potential for industrial production, especially for emulsion polymerization.