Synthesis, characterization, and micellization of PCL-g-PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method
Synthesis, characterization, and micellization of PCL-g-PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method
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DOI：
10.1002/pola.25979
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发表时间：
2012-05
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影响因子：
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通讯作者：
Kai Zhang;Ying Wang;Weipu Zhu;Xiaodong Li;Zhi-quan Shen
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文献类型：
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作者：
Kai Zhang;Ying Wang;Weipu Zhu;Xiaodong Li;Zhi-quan Shen
采用ROP和“点击”化学相结合的方法，在温和条件下通过“接枝到”法制备了生物可降解的PCL-g-PEG两亲性接枝共聚物。首先，以三氟甲磺酸钪为催化剂，通过ε-己内酯（CL）和α-氯代ε-己内酯（CCL）的开环共聚反应，合成了氯代聚ε-己内酯（PCL-Cl）。第二，PCL-Cl的氯基通过NaN 3定量转化为叠氮化物形式。最后，在铜催化下，叠氮功能化的PCL（PCL-N3）与端炔聚乙二醇（A-PEG）发生环加成反应，得到PCL-g-PEG两亲性接枝共聚物。通过1H NMR、FTIR和GPC分析表征了共聚物的组成和接枝结构。这些两亲性接枝共聚物在水溶液中可以自组装成不同直径的球状聚集体，随着接枝密度的增加，球状聚集体的直径减小。© 2012 Wiley Periodicals，Inc. J Polym Sci Part A：Polym Chem，2012
Biodegradable and biocompatible PCL-g-PEG amphiphilic graft copolymers were prepared by combination of ROP and “click” chemistry via “graft onto” method under mild conditions. First, chloro-functionalized poly(e-caprolactone) (PCL-Cl) was synthesized by the ring-opening copolymerization of e-caprolactone (CL) and α-chloro-e-caprolactone (CCL) employing scandium triflate as high-efficient catalyst with near 100% monomer conversion. Second, the chloro groups of PCL-Cl were quantitatively converted into azide form by NaN3. Finally, copper(I)-catalyzed cycloaddition reaction was carried out between azide-functionalized PCL (PCL-N3) and alkyne-terminated poly(ethylene glycol) (A-PEG) to give PCL-g-PEG amphiphilic graft copolymers. The composition and the graft architecture of the copolymers were characterized by 1H NMR, FTIR, and GPC analyses. These amphiphilic graft copolymers could self-assemble into sphere-like aggregates in aqueous solution with diverse diameters, which decreased with the increasing of grafting density. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012