Well‐defined 3‐miktoarm star copolymer 3μ‐HBPE(PCL)₂ (HBPE: hyperbranched polyethylene, PCL: poly[ε‐caprolactone]) was synthesized by combining chain walking polymerization (CWP), ring‐opening polymerization (ROP), and “click” chemistry. The synthetic methodology includes the following steps: (a) synthesis of in‐chain ethynyl‐functionalized PCL, (PCL)₂‐C ≡ CH by ROP of ε‐caprolactone (CL) with ethylene‐functionalized solketal (3‐[prop‐2‐yn‐1‐yloxy] propane‐1,2‐diol) as difunctional initiator and phosphazene superbase t‐BuP₂ as catalyst; (b) synthesis of azido‐functionalized hyperbranched PE (HBPE‐N₃) by CWP of ethylene with α‐diimine‐Pd(II) catalyst, followed by quenching with excess 4‐vinylbenzyl chloride and transformation of chloro to azide group with sodium azide; and (c) “clicking” HBPE‐N₃ and (PCL)₂‐C ≡ CH using copper(I)‐catalyzed azide–alkyne cycloaddition. ¹H NMR spectroscopy, gel permeation chromatography, Fourier‐transform infrared spectroscopy, and differential scanning calorimetry were used to determine the molecular characteristics and thermal properties of the polymers. Self‐assembly behavior of 3μ‐HBPE (PCL)₂ in petroleum ether, a selective solvent for HBPE, was investigated by dynamic light scattering, atomic force microscopy, and transmission electron microscopy. The in‐chain alkyne‐functionalized poly(ε‐caprolactone) is a valuable precursor for PCL‐based complex macromolecular architectures.

中文翻译：

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链内官能化聚（ε-己内酯）：合成含超支化聚乙烯的3-米克臂星的宝贵前体

明确定义的3-杂臂星形共聚物3 μ -HBPE（PCL）₂（HBPE：超支化聚乙烯，PCL：聚[ ε己内酯]）中的溶液通过组合链行走聚合（CWP），开环聚合（ROP）合成和“点击”化学。合成方法包括以下步骤：（a）通过ε-己内酯（CL）和乙烯官能化的缩丁醛（3- [prop-2]的ROP合成链内乙炔基官能化的PCL（PCL）₂ -C≡CH -yn-1氧基]丙烷-1,2-二醇）作为双官能引发剂，磷腈超碱t- BuP ₂作为催化剂; （b）通过乙烯的CWP合成叠氮基官能化的超支化PE（HBPE-N ₃）α-二亚胺-Pd（II）催化剂，然后用过量的4-乙烯基苄基氯淬灭，然后用叠氮化钠将氯转化为叠氮基；（c）使用铜（I）催化的叠氮化物-炔烃环加成反应，“点击” HBPE-N ₃和（PCL）₂ -C≡CH。¹ H NMR光谱，凝胶渗透色谱，傅立叶变换红外光谱和差示扫描量热法用于确定聚合物的分子特性和热性能。3的自组装行为μ -HBPE（PCL）₂通过动态光散射，原子力显微镜和透射电子显微镜研究了石油醚中的六溴环十二烷的选择性溶剂。链内炔基官能化聚（ε-己内酯）是基于PCL的复杂大分子体系结构的宝贵前体。