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Synthesis of well-defined alkyne terminated poly(N-vinyl caprolactam) with stringent control over the LCST by RAFT

机译:用筏子​​对LCST进行严格控制的亚烷基封端的聚(N-乙烯基己内酰胺)的合成

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The reversible addition–fragmentation chain transfer (RAFT) of N -vinyl caprolactam (NVCL) using two new xanthates with alkyne functionalities is reported. The kinetic data obtained for polymerization of this non-activated monomer using a protected alkyne-terminated RAFT agent (PAT-X _(1) ) revealed a linear increase of the polymer molecular weight with the monomer conversion as well as low dispersity ( ? ) during the entire course of the polymerization. The system reported here allowed us to enhance the final conversion, diminish ? and reduce the polymerization temperature compared to the typical values reported in the scarce literature available for the RAFT polymerization of NVCL. The resulting PNVCL was fully characterized using ~(1) H nuclear magnetic resonance ( ~(1) H NMR), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), Fourier-transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) techniques. The temperature-responsive features of PNVCL in aqueous solutions were fully investigated under different conditions using turbidimetry. The presented strategy allows the synthesis of well-defined PNVCL with sharp and reversible phase transition temperatures around 37 °C. By manipulating the polymer molecular weight, or the solution properties, it is possible to tune the PNVCL phase transition. As a proof-of concept, the alkyne functionalized PNVCL was used to afford new linear block copolymers, by reacting with an azide-terminated poly(ethylene glycol) (N _(3) -PEG) through the copper catalyzed azide–alkyne [3 + 2] dipolar cycloaddition (CuAAC) reaction. The results presented establish a robust system to afford the synthesis of PNCVL with fine tuned characteristics that will enable more efficient exploration of the remarkable potential of this polymer in biomedical applications.
机译:据报道了使用两种具有炔磺酸盐的N-vinyl己内酰胺(NVC1)的可逆添加 - 碎片链转移(RAFT)。使用受保护的烷烃封端的筏剂(Pat-X _(1))的该非活化单体聚合的动力学数据显示,具有单体转化率以及低分散性的聚合物分子量的线性增加(?)在整个聚合过程中。在此报告的系统使我们能够提高最终转换,减少?与稀缺文献中报道的典型值相比,降低聚合温度与NVCL的筏聚合的稀缺文献中报道的典型值相比。使用〜(1)H核磁共振(〜(1)H NMR),基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS),傅立叶变换红外光谱,得到的PNVCL完全表征。 (FTIR)和凝胶渗透色谱(GPC)技术。使用浊度测定法在不同条件下全面研究水溶液中PNVCL的温度响应特征。所提出的策略允许在37℃约37℃的尖锐和可逆相变温度合成良好定义的PNVCL。通过操纵聚合物分子量或溶液性能,可以调整PNVCL相转变。作为一种概念证据,通过与叠氮化的聚(乙二醇)(N _(3)-PEG)反应通过铜催化的叠氮化物 - 炔烃[3]通过使新的直线嵌段共聚物提供新的线性嵌段共聚物。[3 + 2]偶极环加成(CUAAC)反应。结果呈现建立稳健的系统,得到PNCV1的合成,其具有微调特性,使得能够更有效地探索这种聚合物在生物医学应用中的显着潜力。

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