本文選題：多齒亞胺配體 + 對(duì)苯二甲醛��； 參考：《東北石油大學(xué)》2016年碩士論文

【摘要】：隨著社會(huì)的發(fā)展,聚乙烯材料在生活中的作用顯得尤為重要,因此,聚乙烯材料的需求量穩(wěn)步上升。催化劑是聚乙烯材料合成過(guò)程中的關(guān)鍵部分,也是其工業(yè)發(fā)展的核心技術(shù)。近些年來(lái),具有多齒配體的金屬配合物在諸多反應(yīng)中均表現(xiàn)出較好的催化性能,尤其在催化乙烯聚合方面有良好的表現(xiàn)。本課題基于多齒亞胺配體及其配合物的設(shè)計(jì),嘗試合成了幾種含有多齒亞胺配體的配合物,并在催化乙烯聚合方面進(jìn)行了初步探索。本課題選用對(duì)苯二甲醛為主要原料,與N-苯基乙二胺、N-甲基乙二胺、鄰苯二胺、間苯二胺、6-氨基-2,4-二甲基吡啶、2,6-二甲基苯胺、2,6-二異丙基苯胺、鄰羥基苯胺、苯肼等幾種胺類(lèi)合成了多齒亞胺配體。利用~1H NMR、~(13)C NMR、IR等分析方法對(duì)已合成配體的結(jié)構(gòu)進(jìn)行表征分析,選用其中產(chǎn)率較高且較為純凈的配體L1、L2、L3、L5合成配合物。本課題選用配體L1,L2與NiBr_2(DME)進(jìn)行絡(luò)合得到雙金屬配合物1a,2a,配體L3和L5分別與NiBr_2(DME)、NiCl_2(DME)進(jìn)行絡(luò)合得到配合物3a、3b、5a、5b。將得到的六種配合物進(jìn)行乙烯聚合試驗(yàn),用倍半乙基氯化鋁為助催化劑,主要考察了常壓條件下不同反應(yīng)溫度以及不同鋁鎳摩爾比對(duì)乙烯聚合行為的影響,并進(jìn)行了動(dòng)力學(xué)分析。雙金屬配合物1a與2a在反應(yīng)溫度為30℃,鋁鎳摩爾比為150時(shí),催化活性達(dá)到最高,聚合產(chǎn)物以低碳齊聚物為主,沒(méi)有高聚物的生成。配合物3a與5a在反應(yīng)溫度為40℃,鋁鎳摩爾比為400時(shí),催化活性達(dá)到最高,聚合產(chǎn)物以輕組分為主,主要為1-丁烯與己烯,有少量的高聚物生成。除此之外,在其他條件相同的情況下,通過(guò)對(duì)配合物3a和3b,5a和5b的對(duì)比發(fā)現(xiàn)配合物中不同鹵原子對(duì)催化性能有較大的影響,含有NiBr_2配合物比含有NiCl_2配合物具有較短的活性誘導(dǎo)期,但壽命相對(duì)較短。
[Abstract]:With the development of society, the function of polyethylene material in life is very important, therefore, the demand of polyethylene material is rising steadily. Catalyst is a key part in the synthesis of polyethylene materials and the core technology of its industrial development. In recent years, metal complexes with polydentate ligands have shown good catalytic performance in many reactions, especially in the catalytic polymerization of ethylene. Based on the design of polydentate imine ligands and their complexes, several complexes containing polydentate imine ligands were synthesized and studied in the field of ethylene polymerization. In this paper, p-benzenediformaldehyde was used as the main raw material, with N-phenylethylenediamine, o-phenylenediamine, m-phenylenediamine 6-amino-2-dimethylpyridyl 2-dimethylaniline, o-hydroxyaniline, 2-dimethylpyridine, 2-diisopropylaniline, o-hydroxyaniline, 4-dimethylpyridine, 4-dimethylpyridine, 2-hydroxyaniline. Polydentate imine ligands were synthesized from several amines such as phenylhydrazine. The structure of the synthesized ligands was characterized by 1H NMR-13C NMR-IR, and the ligand L1, L2, L2, L3, L5, which had higher yield and higher yield, was selected as the synthetic complex. In this paper, the ligand L1C L2 was complexed with NiBr2DMEto to obtain the bimetallic complex 1a2a. the ligand L3 and L5 were complexed with NiBr-2DME-NiCl2DME) to obtain the complex 3a- (3bmb) 5a5b. The ligand L3 and L5 were complexed with NiBr-2DME-NiCl2DME-NiCl2DME. respectively. The ethylene polymerization experiments were carried out on the six complexes. The effects of reaction temperature and Al / Ni molar ratio on ethylene polymerization under atmospheric pressure were investigated. The kinetic analysis was carried out. The catalytic activity of bimetallic complexes 1a and 2a is the highest when the reaction temperature is 30 鈩，

本文編號(hào)：1832380