Facile, efficient routes to diverse protected thiols and to their deprotection and addition to create functional polymers by thiol-ene coupling
Facile, efficient routes to diverse protected thiols and to their deprotection and addition to create functional polymers by thiol-ene coupling
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DOI：
10.1021/ma0718393
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发表时间：
2008-02-26
期刊：
影响因子：
5.5
通讯作者：
Kornfield, Julia A.
中科院分区：
文献类型：
--
作者：
David, R. L. Ameri;Kornfield, Julia A.
通过硫醇-烯加成将咔唑、二硝基苯甲酸酯、苯酚、吡啶和4-氰基-4 '-烷氧基联苯侧基接枝到聚丁二烯（PB）的侧链乙烯基上，得到多分散性与前体材料相当的功能聚合物。开发了清洁（> 90%转化为所需产物）和可扩展的合成方案以将受保护的硫醇基团并入官能前体中。所得乙酰基或苯甲酰基硫酯适合于长期储存，并且在几小时内以不需要分离硫醇中间体的简单程序方便地脱保护并加入到聚合物中。或者，PB官能化可以通过与β-巯基乙醇（BME）反应，随后用合适的酰基卤酯化引入的羟基而同样成功地实现。所描述的化学可潜在地应用于将任何侧基添加到显示乙烯基侧基的任何聚合物、共聚物或嵌段共聚物上。
Carbazole, dinitrobenzoate, phenol, pyridine, and 4-cyano-4 '-alkoxybiphenyl side groups were grafted onto pendant vinyl groups of polybutadiene (PB) by thiol-ene addition to yield functional polymer of polydispersity equal to that of the precursor material. Synthesis protocols that are clean (> 90% conversion to desired product) and scalable were developed to incorporate a protected thiol group into functional precursors. The resulting acetyl or benzoyl thioesters are suitable for long-term storage, and are conveniently deprotected and added to polymer in a matter of hours in a straightforward procedure that does not require isolation of the thiol intermediate. Alternatively, PB functionalization could be achieved with equal success by reaction with P-mercaptoethanol (BME), and subsequent esterification of the incorporated hydroxyl groups with a suitable acyl halide. The chemistry described can potentially be applied to add any side group onto any polymer, copolymer, or block copolymer displaying pendant vinyl groups.