SuFEx Postpolymerization Modification Kinetics and Reactivity in Polymer Brushes
SuFEx Postpolymerization Modification Kinetics and Reactivity in Polymer Brushes
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DOI：
10.1021/acs.macromol.7b02372
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发表时间：
2018-01-23
期刊：
影响因子：
5.5
通讯作者：
Locklin, Jason
中科院分区：
文献类型：
--
作者：
Brooks, Karson;Yatvin, Jeremy;Locklin, Jason
自2014年引入以来，硫(VI)氟化物交换(SuFEx)反应已成为聚合物化学领域中一种很有前途的新反应，无论是在各种聚合物主链的聚合中，还是在聚合后修饰(PPM)中。此前，我们成功地报道了使用SuFEx化学作为一种方法，通过含磺酰氟聚合物刷子的PPM进行表面衍生化。然而，由于该反应提供的条件、底物范围和催化剂选择的多样性，扩大SuFEx在聚合物刷子上用于PPM的用途是有利的，以了解该反应在表面结合方面的优势和局限性。在这项工作中，我们使用了三种不同的聚合物刷子体系，分别与三种不同的硅醚衍生物(芳基、烷基和苯基)反应。这些反应中的每一个都受到不同的催化剂的影响，在此，我们介绍了使用SuFEx化学的聚合物刷子PPM的速度、条件和副产物。此外，我们探索了TBDMS刷子的使用及其与氟磺酸衍生物的反应，令人惊讶的是，没有发生表面反应。通过这些研究，我们能够更好地理解这种点击反应在表面衍生化背景下的速度和局限性。
Since its introduction in 2014, the sulfur(VI) fluoride exchange (SuFEx) reaction has emerged as a promising new reaction in the field of polymer chemistry, in both polymerization of diverse polymer backbones and postpolymerization modification (PPM). Previously, we successfully reported the use of SuFEx chemistry as a method for surface derivatization through the PPM of sulfonyl fluoride containing polymer brushes. However, with the diversity of conditions, substrate scope, and catalyst selection afforded by this reaction, it is advantageous to expand the use of SuFEx for PPM on polymer brushes to discern the advantages and limitations of this reaction in surface conjugation. In this work, we used three different polymer brush systemsalkyl sulfonyl fluorides, aromatic sulfonyl fluorides, and aromatic fluorosulfonatesand each was reacted with three different silyl ether derivatives (aryl, alkyl, and benzyl). Each of these reactions was subjected to different catalysts, and herein, we present rates, conditions, and side products for PPM of polymer brushes using SuFEx chemistry. In addition, we explored the use of TBDMS brushes and their reaction with fluorosulfonate derivatives, where surprisingly no surface reaction occurs. With these studies, we are able to better understand the rates and limitations of this click reaction in the context of surface derivatization.