Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes
Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes
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DOI：
10.1039/c9py01123d
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发表时间：
2019-09-28
影响因子：
4.6
通讯作者：
Patton, Derek L.
中科院分区：
文献类型：
--
作者：
Reese, Cassandra M.;Thompson, Brittany J.;Patton, Derek L.
硫代内酯化学作为一种强大的聚合后改性（PPM）途径得到了广泛的关注。在这里，我们通过氨基水解和硫醇介导的含硫内酯聚合物刷的双重修饰，将这种多功能化学应用于超薄多功能聚合物表面的制造。采用微波辅助表面聚合法制备了dl -同型半胱氨酸硫内酯丙烯酰胺的聚合物刷状表面。通过与溴苄胺和1H，1H-全氟- n -癸基丙烯酸酯的顺序反应和单锅反应，探索了硫代内酯功能刷的氨解和硫- michael双改性。x射线光电子能谱和氩气簇离子溅射深度剖面可以定量比较顺序和一锅PPM路线在整个电刷厚度上固定的官能团的转换和空间分布。虽然一锅条件被证明在固定刷内的胺和丙烯酸酯方面更有效，但顺序反应使得使用反应性微接触印刷制造多功能微图案刷表面成为可能。
Thiolactone chemistry has garnered significant attention as a powerful post-polymerization modification (PPM) route to mutlifunctional polymeric materials. Here, we apply this versatile chemistry to the fabrication of ultrathin, multifunctional polymer surfaces via aminolysis and thiol-mediated double modifications of thiolactone-containing polymer brushes. Polymer brush surfaces were synthesized via microwave-assisted surface-initiated polymerization of DL-homocysteine thiolactone acrylamide. Aminolysis and thiol-Michael double modifications of the thiolactone-functional brush were explored using both sequential and one-pot reactions with bromobenzyl amine and 1H,1H-perfluoro-N-decyl acrylate. X-ray photoelectron spectroscopy and argon gas cluster ion sputter depth profiling enabled quantitative comparison of the sequential and one-pot PPM routes with regard to conversion and spatial distribution of functional groups immobilized throughout thickness of the brush. While one-pot conditions proved to be more effective in immobilizing the amine and acrylate within the brush, the sequential reaction enabled the fabrication of multifunctional, micropatterned brush surfaces using reactive microcontact printing.