本文選題：β-酮亞胺配體 + β-二酮亞胺配體　； 參考：《大連理工大學(xué)》2014年碩士論文

【摘要】：聚己內(nèi)酯(PCL)是一類具有良好生物活性的聚合材料,由于其自身的可透過(guò)性、易降解性而廣泛應(yīng)用于生命科學(xué)和藥物科學(xué)領(lǐng)域。合成聚己內(nèi)酯的一種主要方法是以金屬絡(luò)合物為催化劑引發(fā)內(nèi)酯發(fā)生開環(huán)聚合反應(yīng)得到,而通過(guò)調(diào)變金屬絡(luò)合物金屬中心和配體本身的種類和結(jié)構(gòu),可以實(shí)現(xiàn)內(nèi)酯的可控開環(huán)聚合。目前對(duì)于催化ε-己內(nèi)酯的開環(huán)聚合反應(yīng)的金屬絡(luò)合物催化劑的研究已經(jīng)很常見,但由于大多數(shù)金屬催化劑的金屬殘留可能存在毒性,限制了聚己內(nèi)酯的進(jìn)一步應(yīng)用。因此研究低毒甚至無(wú)毒的生物相容性的金屬有機(jī)催化劑,實(shí)現(xiàn)健康環(huán)保的催化ε-己內(nèi)酯開環(huán)聚合具有極其重大的意義。 本論文選用FeCl2(THF)1.5與N-烷基筇-酮亞胺或二酮亞胺配體(nacac或nacnac)反應(yīng),得到N-烷基-β-亞胺或二酮亞胺鐵金屬催化劑,并考察它們催化ε-己內(nèi)酯開環(huán)聚合反應(yīng)的催化活性。具體結(jié)果如下：反應(yīng)得到一系列的雙配體配位的鐵絡(luò)合物nacacR2Fe(R=iPr,3b;Bu,3c；CHPh2,3e；ad,3f), nacnacR2Fe(R=CH3,4a;iPr,4b；tBu,4c; CH2CH2Ph,4d)以及三核鐵絡(luò)合物[nacacCH32Fe]3Li2O(5a)。由于得到的絡(luò)合物中鐵原子自身的順磁作用,無(wú)法用核磁共振作為絡(luò)合物結(jié)構(gòu)的直接表征依據(jù),但這些絡(luò)合物通過(guò)紅外光譜以及高分辨質(zhì)譜進(jìn)行表征,其中絡(luò)合物3c,4a,4c,4d和5a的分子結(jié)構(gòu)通過(guò)X-單晶衍射進(jìn)行了確定,5a還經(jīng)過(guò)原子光譜進(jìn)行金屬元素含量分析。實(shí)驗(yàn)證明,這些鐵絡(luò)合物對(duì)于ε-己內(nèi)酯開環(huán)聚合反應(yīng)均具有催化活性。其中雙配體配位的單核鐵絡(luò)合物3b、3c、3e和3f,在80℃下,1h內(nèi)催化ε-己內(nèi)酯開環(huán)聚合反應(yīng)單體轉(zhuǎn)化率均可達(dá)到99%。此外,三核鐵絡(luò)合物5a催化活性最好,在8℃條件下,5min內(nèi)即可實(shí)現(xiàn)99%的單體轉(zhuǎn)化率；258下,100min內(nèi)ε-己內(nèi)酯單體轉(zhuǎn)化率達(dá)到98%,并且相應(yīng)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，

本文編號(hào)：1745862