多齿亚胺配体的合成及应用探索

发布时间：2018-05-02 04:34

  本文选题：多齿亚胺配体 + 对苯二甲醛　； 参考：《东北石油大学》2016年硕士论文

【摘要】：随着社会的发展,聚乙烯材料在生活中的作用显得尤为重要,因此,聚乙烯材料的需求量稳步上升。催化剂是聚乙烯材料合成过程中的关键部分,也是其工业发展的核心技术。近些年来,具有多齿配体的金属配合物在诸多反应中均表现出较好的催化性能,尤其在催化乙烯聚合方面有良好的表现。本课题基于多齿亚胺配体及其配合物的设计,尝试合成了几种含有多齿亚胺配体的配合物,并在催化乙烯聚合方面进行了初步探索。本课题选用对苯二甲醛为主要原料,与N-苯基乙二胺、N-甲基乙二胺、邻苯二胺、间苯二胺、6-氨基-2,4-二甲基吡啶、2,6-二甲基苯胺、2,6-二异丙基苯胺、邻羟基苯胺、苯肼等几种胺类合成了多齿亚胺配体。利用~1H NMR、~(13)C NMR、IR等分析方法对已合成配体的结构进行表征分析,选用其中产率较高且较为纯净的配体L1、L2、L3、L5合成配合物。本课题选用配体L1,L2与NiBr_2(DME)进行络合得到双金属配合物1a,2a,配体L3和L5分别与NiBr_2(DME)、NiCl_2(DME)进行络合得到配合物3a、3b、5a、5b。将得到的六种配合物进行乙烯聚合试验,用倍半乙基氯化铝为助催化剂,主要考察了常压条件下不同反应温度以及不同铝镍摩尔比对乙烯聚合行为的影响,并进行了动力学分析。双金属配合物1a与2a在反应温度为30℃,铝镍摩尔比为150时,催化活性达到最高,聚合产物以低碳齐聚物为主,没有高聚物的生成。配合物3a与5a在反应温度为40℃,铝镍摩尔比为400时,催化活性达到最高,聚合产物以轻组分为主,主要为1-丁烯与己烯,有少量的高聚物生成。除此之外,在其他条件相同的情况下,通过对配合物3a和3b,5a和5b的对比发现配合物中不同卤原子对催化性能有较大的影响,含有NiBr_2配合物比含有NiCl_2配合物具有较短的活性诱导期,但寿命相对较短。
[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，

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