本文關(guān)鍵詞：單（雙）核鋁絡(luò)合物的合成及催化性能研究　出處：《大連理工大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

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【摘要】：聚己內(nèi)酯(PCL)是性能優(yōu)良的脂肪族聚酯,目前主要通過(guò)使用金屬化合物催化己內(nèi)酯的開(kāi)環(huán)聚合制備。由于其具有良好的生物相容性,細(xì)胞可以在其基架上正常生長(zhǎng),并且具有可滲透性以及可降解性,因此在生物醫(yī)學(xué)和制藥工業(yè)中有著重要而廣泛的應(yīng)用前景。近年來(lái),研究工作者不斷開(kāi)發(fā)出各種金屬有機(jī)絡(luò)合物,通過(guò)選擇合適的金屬和配體以實(shí)現(xiàn)己內(nèi)酯高效、可控的聚合。盡管目前可用于催化ε-己內(nèi)酯開(kāi)環(huán)聚合反應(yīng)的金屬絡(luò)合物種類繁多,但能實(shí)現(xiàn)高效、可控的催化體系還很少,并且多數(shù)催化劑并不穩(wěn)定,部分催化體系不僅價(jià)格昂貴而且毒性較大,限制了其應(yīng)用。因此研究開(kāi)發(fā)低毒并且高效的催化體系,對(duì)促進(jìn)聚己內(nèi)酯的發(fā)展應(yīng)用具有非常重要的意義。 本論文選用低毒性并且含量豐富的鋁金屬作為催化金屬中心原子,合成了11個(gè)新N-烷基-β-酮亞胺和二酮亞胺鋁絡(luò)合物催化劑,并考察了其催化ε-己內(nèi)酯開(kāi)環(huán)聚合性能。具體實(shí)驗(yàn)結(jié)果如下：制備了一系列的β-酮亞胺鋁絡(luò)合物NacacR alEtCl(R=tBu,2a;iPr,2b;CH3,2c),β-二酮亞胺鋁絡(luò)合物NacnacR AlEtCl (R=tBu,3c;iPr,3d; Bn,3e), NacnacRAl(CH2SiMe3)Cl (R=tBu,4a;iPr,4b),和氧橋聯(lián)雙核鋁絡(luò)合物[NacnacR AlEt]2(μ-O)(R=tBu,5a;iPr,5b),[NacnaciPr AlCl]2(μ-O)(5c),這些絡(luò)合物通過(guò)1H NMR,13C NMR, EI-MS進(jìn)行了表征,其中絡(luò)合物5a的分子結(jié)構(gòu)通過(guò)X-單晶衍射進(jìn)行了確定。實(shí)驗(yàn)結(jié)果證明這些鋁絡(luò)合物均可以催化ε-己內(nèi)酯的開(kāi)環(huán)聚合反應(yīng),其中絡(luò)合物4a表現(xiàn)出最高的催化活性,在單體與催化劑摩爾濃度比例為100：1時(shí),以甲苯為溶劑,在80℃條件下反應(yīng)10分鐘即可獲得數(shù)均分子量為4.12×104,分子量分布(PDD為1.06的聚己內(nèi)酯,單體轉(zhuǎn)化率達(dá)到98%。
[Abstract]:Polycaprolactone (PCL) is a kind of aliphatic polyester with excellent properties. At present, it is mainly prepared by using metal compounds to catalyze the ring-opening polymerization of caprolactone, because of its good biocompatibility. Cells can grow normally on its base, and have permeability and degradability, so it has important and extensive application prospect in biomedicine and pharmaceutical industry in recent years. Researchers have been developing various organometallic complexes to achieve high efficiency of caprolactone by selecting suitable metal and ligand. Controlled polymerization. Although there are many kinds of metal complexes which can be used to catalyze the ring-opening polymerization of 蔚 -caprolactone, there are few catalytic systems which can achieve high efficiency and controllable, and most of the catalysts are unstable. Part of the catalytic system is expensive and toxic, which limits its application. Therefore, the research and development of low toxicity and high efficiency catalytic system is of great significance to promote the development and application of polycaprolactone. In this thesis, 11 new N- alkyl-尾-keto-imide and diketo-imine aluminum complex catalysts were synthesized by using low toxicity and abundant aluminum metal as the central atoms of the catalyst. The catalytic properties of 蔚 -caprolactone ring-opening polymerization were also investigated. The experimental results were as follows: a series of 尾 -keto-imide aluminum complexes, NacacR alEtCl-rtButBu2a, were prepared. IPRA 2b; Ch _ 3N _ 2c, 尾 -diketo-imine aluminum complex NacnacR AlEtCl ~ (3) C; IPrn 3 d; BNP 3e, NacnacRAl(CH2SiMe3)Cl TBU 4a; IPRA 4bN, and oxygen bridged binuclear aluminum complex [NacnacR AlEt. [The complexes were characterized by 1H NMR-13C NMRs, EI-MS. The molecular structure of the complex 5a was determined by X-ray diffraction. The experimental results show that these aluminum complexes can catalyze the ring-opening polymerization of 蔚 -caprolactone. The complex 4a showed the highest catalytic activity. Toluene was used as solvent when the molar ratio of monomer to catalyst was 100: 1. Poly (caprolactone) with a number average molecular weight of 4.12 脳 10 ~ 4 and a molecular weight distribution of 1.06 was obtained at 80 鈩，

本文編號(hào)：1426288