β-酮亚胺和二酮亚胺铁络合物的合成及其催化性能

发布时间：2018-04-13 19:24

  本文选题：β-酮亚胺配体 + β-二酮亚胺配体　； 参考：《大连理工大学》2014年硕士论文

【摘要】：聚己内酯(PCL)是一类具有良好生物活性的聚合材料,由于其自身的可透过性、易降解性而广泛应用于生命科学和药物科学领域。合成聚己内酯的一种主要方法是以金属络合物为催化剂引发内酯发生开环聚合反应得到,而通过调变金属络合物金属中心和配体本身的种类和结构,可以实现内酯的可控开环聚合。目前对于催化ε-己内酯的开环聚合反应的金属络合物催化剂的研究已经很常见,但由于大多数金属催化剂的金属残留可能存在毒性,限制了聚己内酯的进一步应用。因此研究低毒甚至无毒的生物相容性的金属有机催化剂,实现健康环保的催化ε-己内酯开环聚合具有极其重大的意义。 本论文选用FeCl2(THF)1.5与N-烷基筇-酮亚胺或二酮亚胺配体(nacac或nacnac)反应,得到N-烷基-β-亚胺或二酮亚胺铁金属催化剂,并考察它们催化ε-己内酯开环聚合反应的催化活性。具体结果如下：反应得到一系列的双配体配位的铁络合物nacacR2Fe(R=iPr,3b;Bu,3c；CHPh2,3e；ad,3f), nacnacR2Fe(R=CH3,4a;iPr,4b；tBu,4c; CH2CH2Ph,4d)以及三核铁络合物[nacacCH32Fe]3Li2O(5a)。由于得到的络合物中铁原子自身的顺磁作用,无法用核磁共振作为络合物结构的直接表征依据,但这些络合物通过红外光谱以及高分辨质谱进行表征,其中络合物3c,4a,4c,4d和5a的分子结构通过X-单晶衍射进行了确定,5a还经过原子光谱进行金属元素含量分析。实验证明,这些铁络合物对于ε-己内酯开环聚合反应均具有催化活性。其中双配体配位的单核铁络合物3b、3c、3e和3f,在80℃下,1h内催化ε-己内酯开环聚合反应单体转化率均可达到99%。此外,三核铁络合物5a催化活性最好,在8℃条件下,5min内即可实现99%的单体转化率；258下,100min内ε-己内酯单体转化率达到98%,并且相应的聚合物分子量分布很窄(PDI=1.06-1.28)。
[Abstract]:Polycaprolactone (PCL) is a kind of polymeric materials with good bioactivity. It is widely used in life science and pharmaceutical science because of its own permeability and degradability.One of the main methods for the synthesis of polycaprolactone is the ring-opening polymerization of lactones initiated by metal complexes, and the modification of the metal centers of metal complexes and the structure of the ligands themselves.The controlled ring-opening polymerization of lactone can be realized.The studies on metal complex catalysts for ring-opening polymerization of 蔚 -caprolactone have been very common, but the further application of polycaprolactone is limited due to the toxicity of metal residues in most metal catalysts.Therefore, it is of great significance to study low toxicity or even nontoxic biocompatible organometallic catalysts to realize healthy and environmentally friendly ring-opening polymerization of 蔚 -caprolactone.In this paper, FeCl2(THF)1.5 was used to react with N-alkyl Qiongkeimide or diketo-imine ligand, nacac or nacnacc) to obtain N-alkyl- 尾 -imine or diketo-imine iron metal catalysts, and their catalytic activity for ring-opening polymerization of 蔚 -caprolactone was investigated.Due to the paramagnetic interaction of the iron atoms in the complex, it is not possible to use NMR as the basis for the direct characterization of the complex structure, but these complexes are characterized by infrared spectroscopy and high resolution mass spectrometry.The molecular structures of the complex 3cz4a4cf4d and 5a have been determined by X-ray diffraction and the content of metal elements has been analyzed by atomic spectra.The experimental results show that these iron complexes have catalytic activity for ring-opening polymerization of 蔚-caprolactone.Among them, the mononuclear iron complexes with double ligands 3bn3cn3e and 3fcan catalyze the monomer conversion of 蔚 -caprolactone ring-opening polymerization at 80 鈩，

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