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主族金属配合物的合成、表征及其在环酯开环聚合中的应用

Synthesis, Characterization of Main-group Metal Complexes and Application in ROP of Cyclic Esters

【作者】 潘效波

【导师】 唐宁; 邬金才;

【作者基本信息】 兰州大学 , 无机化学, 2010, 博士

【摘要】 过去三十年,高分子聚酯是一种被广泛应用于薄膜、纤维、服装等领域的合成材料。由于聚酯类高分子尤其聚己内酯(PCL),聚乳交酯(PLA),以及它们的共聚物具有良好的生物相容性、无毒、降解性可调,符合医药用高分子材料的要求,使其在骨折内外固定、手术缝合线、组织工程支架及药物控制释放的载体材料等方面的应用受到广泛的关注。生物降解和相容的聚酯材料PLA的原材料来源于玉米,甜菜以及可其他的循环农产品。随着科技的发展和社会的进步,这种可再生及环境友好的聚酯可逐渐取代日益枯竭的石油化工产品而越来越显得重要。因此这类生物降解聚酯的合成方法具有很高的研究价值。本论文主要针对聚酯的催化合成进行了研究。本论文由四部分组成:第一章主要介绍了的环酯开环聚合的研究现状。第二章描述了一个新颖的类Salen-Al配合物的合成、表征和开环聚合的性质研究。结果表明,类Salen-Al配合物是一个对乳交酯的开环聚合反应具有很好的催化活性,聚酯的分子量可以精确控制且分子量分布度小,并且对外消旋乳交酯的开环聚合表现出一定的立体选择性。第三章描述了以EDBPH2为配体的一系列双金属配合物的合成、表征和催化开环聚合的性质研究。实验结果表明,部分双金属配合物是对乳交酯的开环聚合反应具有较高的催化活性和一定的立体选择性。第四章描述了以EDBPH2为配体的烷氧铝-钠双金属配合物及反冠醚配合物的合成、表征和催化开环聚合的性质研究。实验结果表明,烷氧铝-钠双金属配合物是对己内酯的开环聚合反应具有一定的催化活性。并且通过设计不同的实验对氧核的来源作了详细的讨论,为反冠醚的合成提供一些经验和帮助。

【Abstract】 Polyesters are among the most versatile synthetic polymers, and they have been widely used as fibers, plastics and coatings. Over the past three decades, polyesters, especially polylactide (PLA), polycaprolactone (PCL) and their copolymers, have attracted considerable attention due to their new biomedical and pharmaceutical applications such as biodegradable surgical sutures and postoperative support pins and splints, or as a delivery medium for controlled release of drugs. The starting materials for biodegradable and bioassimilable PLA are derived from corn, beets, and other annually renewable resources. As the depletion of petrochemical feedstock comes near, the renewable and environmentally friendly polymers are increasingly important for a sustainable future, so such synthesis of biodegradable polyesters possess higher research value. This paper focuses on studying the synthesis of polyesters.This paper consists of four chapters1. It was given a brief review of ring-opening polymerization about cyclic esters.2. Synthesized and characterized one novel aluminium complex like Salen supported by a sulfonamide/Shiff base ligand and the application in ring-opening polymerization of lactide. Experimental results show that aluminium complex is an efficient initiator for the ring-opening polymerization of lactide in controlled fashion, yielding polymers with expectative molecular weight and low polydispersity indexes. Furthermore, aluminium complex has isotactic selectivity for the ring-opening polymerization of rac-lactide.3. Synthesized and characterized a series novel bulky hetero-bimetallic aryloxides supported by EDBPH2 ligand and the application in ring-opening polymerization of lactide. Experimental results show that some hetero-bimetallic aryloxides are an efficient initiator for the ring-opening polymerization of lactide in controlled fashion, yielding polymers low polydispersity indexes and have slight isotactic stereo selectivity for the ring-opening polymerization of rac-lactide.4. Synthesized and characterized a series novel sodium-aluminum complexes and a novel sodium-aluminum inverse crown ether (ICE) complex supported by EDBPH2 ligand and the application in ring-opening polymerization of lactide. Experimental results show that one sodium-aluminum complex is an efficient initiator for the ring-opening polymerization of s-caprolactone. Furthermore, the source of anion oxo has been discussed through different experiments in detail for future research of inverse crown ether to provide some experience.

  • 【网络出版投稿人】 兰州大学
  • 【网络出版年期】2010年 10期
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