Abstract Metal-free catalysis was successfully applied to polymerize ω-pentadecalactone (PDL) by ring-opening polymerization (ROP) using several amino-ended initiators, namely hexylamine, allylamine and O,O′-bis(3-aminopropyl)diethylene glycol. This polymerization method was suitable to prepare telechelic polyesters carrying functional-end groups. The technique was then extended to the synthesis of block copolymers by ROP of PDL using bisamino-ended poly(ethylene glycol) (Mn = 2600) as macroinitiator. PPDLx-PEG56-PPDLx triblock copolymers with Mn ranging between ∼4000 and ∼90,000 g ·mol−1 were synthesized and extensively characterized by NMR, DSC, TGA and XRD. The amphiphilic copolymers thus produced were demonstrated to be able to self-assemble in nanoparticles with average diameters of ∼100–200 nm and morphologies highly depending on blocks lengths. The described synthetic route distinguishes in providing “clean” amphiphilic copolymers, which are attractive candidates for biomedical applications.

中文翻译：

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使用氨基末端引发剂的 ω-十五内酯的无金属催化开环聚合和嵌段共聚

摘要 以己胺、烯丙胺和O,O'-双(3-氨基丙基)二甘醇为原料，在无金属催化作用下，通过开环聚合(ROP)成功地聚合了ω-十五内酯(PDL)。该聚合方法适用于制备带有端基官能团的遥爪聚酯。然后将该技术扩展到使用双氨基末端聚（乙二醇）（Mn = 2600）作为大分子引发剂通过 PDL 的 ROP 合成嵌段共聚物。PPDLx-PEG56-PPDLx 三嵌段共聚物的Mn 范围在~4000 和~90,000 g·mol-1 之间，并通过NMR、DSC、TGA 和XRD 进行了广泛表征。由此产生的两亲共聚物被证明能够自组装成平均直径约为 100-200 nm 的纳米颗粒，并且形态高度取决于嵌段长度。所描述的合成路线的区别在于提供“清洁”的两亲共聚物，这是生物医学应用的有吸引力的候选者。