Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates
Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates
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DOI：
10.1021/acs.macromol.7b01603
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发表时间：
2017-09
期刊：
影响因子：
5.5
通讯作者：
Janina-Miriam Noy;A. Friedrich;K. Batten;Mathamsanqa N. Bhebhe;N. Busatto;Rhiannon Batchelor;A. Kristanti;Yiwen Pei;P. Roth
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文献类型：
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作者：
Janina-Miriam Noy;A. Friedrich;K. Batten;Mathamsanqa N. Bhebhe;N. Busatto;Rhiannon Batchelor;A. Kristanti;Yiwen Pei;P. Roth
提出了一种进行高效对氟取代反应的甲基丙烯酸聚合物。通过RAFT工艺制备了一系列结构明确的聚(2,3,4,5,6-甲基丙烯酸五氟苄酯)(pPFBMA)均聚物，其聚合度为28至132，且Đ≤1.29。 pPFBMA 样品是无规立构的（在 1H 和 19F NMR 谱中具有明显的三单元组立构规整度）并且可溶于大多数有机溶剂。 pPFBMA 通过对氟取代与一系列硫醇（通常为 1.1 当量的硫醇、碱、RT，<1 小时）进行定量反应，没有观察到任何副反应。用不同的（硫代）羰基硫试剂进行对氟取代是可能的，并且允许随后一锅法裂解二硫酯侧基并同时进行硫杂-迈克尔侧基修饰。与脂肪胺的反应（通常为 2.5 当量胺，50–60 °C，过夜）导致对氟化物完全取代，而没有观察到任何酯裂解反应。然而，对于伯胺，H2NR，...
A methacrylic polymer undergoing highly efficient para-fluoro substitution reactions is presented. A series of well-defined poly(2,3,4,5,6-pentafluorobenzyl methacrylate) (pPFBMA) homopolymers with degrees of polymerization from 28 to 132 and Đ ≤ 1.29 was prepared by the RAFT process. pPFBMA samples were atactic (with triad tacticity apparent in 1H and 19F NMR spectra) and soluble in most organic solvents. pPFBMA reacted quantitatively through para-fluoro substitution with a range of thiols (typically 1.1 equiv of thiol, base, RT, <1 h) in the absence of any observed side reactions. Para-fluoro substitution with different (thio)carbonylthio reagents was possible and allowed for subsequent one-pot cleavage of dithioester pendent groups with concurrent thia-Michael side group modification. Reactions with aliphatic amines (typically 2.5 equiv of amine, 50–60 °C, overnight) resulted in complete substitution of the para-fluorides without any observed ester cleavage reactions. However, for primary amines, H2NR,...