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 systems—alkyl sulfonyl fluorides, aromatic sulfonyl fluorides, and aromatic fluorosulfonates—and 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.

中文翻译：

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SuFEx聚合物刷中的后聚合改性动力学和反应性

自2014年推出以来，氟化硫（VI）交换（SuFEx）反应已成为聚合物化学领域中一种有希望的新反应，包括多种聚合物主链的聚合和后聚合改性（PPM）。以前，我们成功地报告了使用SuFEx化学方法作为通过含磺酰氟的聚合物刷的PPM进行表面衍生化的方法。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，有利的是扩展SuFEx在聚合物刷上用于PPM的用途，以识别该反应在表面共轭中的优点和局限性。在这项工作中，我们使用了三种不同的聚合物刷系统-烷基磺酰氟，芳族磺酰氟，和芳族氟磺酸盐-分别与三种不同的甲硅烷基醚衍生物（芳基，烷基和苄基）反应。这些反应中的每一个都使用不同的催化剂，在这里，我们介绍了使用SuFEx化学方法制备聚合物刷的PPM的速率，条件和副产物。此外，我们探索了TBDMS刷的使用及其与氟代磺酸盐衍生物的反应，令人惊讶的是没有发生表面反应。通过这些研究，我们能够更好地了解表面衍生化过程中这种点击反应的发生率和局限性。我们探索了TBDMS刷子的使用及其与氟代磺酸盐衍生物的反应，令人惊讶的是没有发生表面反应。通过这些研究，我们能够更好地了解表面衍生化过程中这种点击反应的发生率和局限性。我们探索了TBDMS刷子的使用及其与氟代磺酸盐衍生物的反应，令人惊讶的是没有发生表面反应。通过这些研究，我们能够更好地了解表面衍生化过程中这种点击反应的发生率和局限性。