Side-chain poly(phosphoramidate)s via acyclic diene metathesis polycondensation
Side-chain poly(phosphoramidate)s via acyclic diene metathesis polycondensation
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DOI：
10.1039/c6py00999a
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发表时间：
2016-01-01
影响因子：
4.6
通讯作者：
Wurm, Frederik R.
中科院分区：
文献类型：
--
作者：
Cankaya, Alper;Steinmann, Mark;Wurm, Frederik R.
聚（磷酸酯）（PPE）是有趣的可降解多功能聚合物。在这里，我们首次通过无环二烯复分解（ADMET）缩聚合成聚（氨基磷酸酯）（PPA），侧链中带有酰胺键。与传统的聚酰胺相比，磷酰胺中的 P-N 键比相应的酯更不稳定。将不饱和 PPA 与 PPE 的结构类似物进行了比较：两种新型 α,.-二烯，即。 e.双(十一烯-10-基)-正丁基-氨基磷酸酯(1) 和双(十一烯-10-基)-正丁基-磷酸酯(2) 通过格鲁布斯型催化剂聚合成分子量高达约100 的聚合物。 20 000 克摩尔(-1)。氢化后获得类聚乙烯结构，其中氨基磷酸酯或酯代表精确放置的缺陷。通过差示扫描量热法 (DSC) 和热重分析 (TGA) 将 PPA 与其 PPE 类似物的热行为和稳定性进行比较，结果显示饱和材料的结晶行为相似，但不饱和 PPA 与 PPE 存在显着差异。通过 ADMET 聚合合成 PPA 为各种 PPA 提供了一种有趣的方法。水解不稳定的氨基磷酸酯侧基进一步为开发可水解降解材料或作为通常表现出有限溶解度的聚(磷酸二酯)的可加工中间体提供了可能性。
Poly(phosphoester)s (PPEs) are interesting degradable multi-functional polymers. Here, we present the first synthesis of poly(phosphoramidate) s (PPAs) via acyclic diene metathesis (ADMET) polycondensation with amidate linkages in side chains. In contrast to conventional polyamides, the P-N-bond in phosphor-amidates is more labile than the corresponding esters. Unsaturated PPAs were compared with structural analogues of PPEs: two novel a,.-dienes, i. e. bis-(undecen-10-yl)-n-butyl-phosphoramidate (1) and bis( undecen-10-yl)-n-butyl-phosphate (2) have been polymerized by Grubbs-type catalysts to polymers with molecular weights up to ca. 20 000 g mol(-1). After hydrogenation polyethylene-like structures were obtained with the phosphoramidate or -ester representing a precisely placed defect. PPAs were compared to their PPE analogues with respect to their thermal behavior and stability by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), showing similar crystallization behavior for the saturated materials, but significant differences for unsaturated PPA vs. PPE. This synthesis of PPAs via ADMET polymerization offers an interesting approach to various PPAs. The hydrolytically labile pendant phosphoramidate further offers the possibility for the development of hydrolytically degradable materials or as processable intermediates for poly(phosphodiester) s which often show limited solubility.