扇型-线型结构的生物降解高分子嵌段共聚物的设计、合成与性能-材料学专业论文.docxVIP

上海交通大学硕士毕业论文 上海交通大学硕士毕业论文 II II 接着，将产物作为大分子引发剂，来引发NCA-BLG的开环聚合。为表征嵌 段的物理特性，我们采用红外、核磁、基质辅助解离飞行时间质谱、凝胶 渗透色谱、示差量热和广角X射线衍射的方法。 据我们所知，这是第一次报道通过开环聚合和Click化学方法合成线型- 扇型PCL基的不对称嵌段聚合物。据此，我们开拓了另外一种合成生物降 解和仿生的聚酯基生物材料的方法。 关键词: 不对称; 线型-扇型; 聚己内酯; 聚氨基酸;开环聚合; Click 化学 PAGE PAGE IV Design, Synthesis and Characterization of Linear- Dendron-Like Biodegradable Block Co-polymers ABSTRACT Based on biodegradable polyester PCL as precursor, combining PEO or PBLG and introducing the asymmetry” concept, we obtained a series of linear-dendron-like biodegradable block copolymers. The crystallization and self-assembly property were in detail characterized. Synthesis and Characterization of Linear-Dendron-like PCL-b-PEO Copolymers via the Combination of Ring-Opening Polymerization and Click Chemistry A new class of linear-dendron-like PCL-b-PEO copolymers was synthesized via controlled ring-opening polymerization (ROP) of ?-caprolactone (CL) followed by a click conjugation with azide-terminated PEO (PEO-N3). The dendron-like PCL terminated with a clickable alkyne group (Dm-PCL, m = 0, 1, 2, and 3) was for the first time synthesized from the ROP of CL monomer using a propargyl focal point dendrons (Dm) as the initiators and stannous octoate as catalyst in bulk at 130℃. Then, the linear-dendron-like PCL-b-PEO copolymers (Dm-PCL-b-PEO) were obtained by the click conjugation of Dm-PCL with PEO-N3 using PMDETA/CuBr in DMF solution at 35℃. Their molecular structures and physical properties were in detail characterized by FT-IR, NMR, MALLS-GPC, DSC, WAXD, and POM. Moreover, the biodegradable micelles and vesicles with different sizes (less than 100 nm) were easily fabricated from these PCL-b-PEO copolymers in aqueous solution, and both the PEO composition and the linear-dendron-like architecture of copolymers controlled the morphology and the average size of self-assembled nanoparticles. A Versatile Strategy for the Synthesis of Dendron-like Polypeptide/Linear Poly(?-caprolactone) Block Copolymers vi