超支化镍催化剂取代基对乙烯齐聚性能的影响
发布时间：2018-11-26 08:00
【摘要】：本论文以十二胺为支链合成了超支化聚酰胺-胺大分子,再分别与3-甲基水杨醛、3-叔丁基水杨醛、3-甲氧基水杨醛进行席夫碱反应合成系列超支化取代水杨醛配体,三种超支化取代水杨醛配体分别与六水氯化镍进行络合,得到系列超支化取代水杨醛镍配合物;采用红外光谱、紫外光谱、核磁氢谱(1H-NMR)和电喷雾电离质谱(ESI-MS)表征手段对系列超支化取代水杨醛配体和系列超支化取代水杨醛镍配合物进行结构表征,并且考察了系列超支化取代水杨醛镍配合物催化乙烯齐聚反应的性能,并初步探索超支化取代水杨醛镍配合物的取代基效应对催化剂性能的影响。以甲苯为溶剂,分别以甲基铝氧烷(MAO)、一氯二乙基铝(DEAC)、倍半乙基氯化铝(EASC)为助催化剂,考察超支化取代水杨醛镍系催化剂的乙烯齐聚性能。实验结果表明,在Al/Ni摩尔比为500、反应压力为0.5MPa、反应时间为30min、反应温度为25℃的聚合条件下,以MAO和DEAC为助催化剂时超支化镍系催化剂的活性为104 g mol-1 h-1数量级、以EASC为助催化剂时的活性为106 g mol-1 h-1数量级,并且在EASC为助催化剂时产物中出现奇数碳产物。研究发现,在三种助催化剂条件下,系列超支化取代水杨醛镍配合物催化剂的活性和高碳烯烃选择性顺序由高到低为:超支化甲氧基水杨醛镍配合物,超支化叔丁基水杨醛镍配合物,超支化甲基水杨醛镍配合物。为了深入研究超支化水杨醛镍系催化剂的反应机理,定量分析超支化镍系催化剂活性的调控因素,对超支化镍系催化剂在乙烯齐聚反应中的行为进行了简单的表观反应动力学研究,采用最小二乘法进行线性回归作图,得到反应速率关于反应压力、催化剂的浓度的表观反应级数,并且求得反应活化能,进而建立三种催化剂的表观动力学方程。
[Abstract]:In this paper, a series of hyperbranched polyamide-amine macromolecules were synthesized by Schiff base reaction with 3-methylsalicylaldehyde, 3- tert-Ding Ji salicylaldehyde and 3-methoxy salicylaldehyde, respectively, using dodecylamine as branching chain to synthesize a series of hyperbranched substituted salicylaldehyde ligands. Three kinds of hyperbranched substituted salicylaldehyde ligands were complexed with nickel chloride hexahydrate to obtain a series of hyperbranched substituted salicylic aldehydes nickel complexes. A series of hyperbranched substituted salicylaldehyde ligands and a series of hyperbranched substituted salicylaldehyde-nickel complexes were characterized by IR, UV, 1H-NMR and ESI-MS. The catalytic properties of a series of hyperbranched substituted salicylaldehyde-nickel complexes for ethylene oligomerization were investigated, and the influence of the substituent group effect of the hyperbranched substituted salicylaldehyde-nickel complexes on the catalytic performance was preliminarily investigated. The ethylene oligomerization of hyperbranched substituted salicylaldehyde-nickel catalyst was investigated with toluene as solvent and methyl aluminoxane (MAO), chlorodiethyl aluminum (DEAC), times hemiethyl aluminum chloride (EASC) as co-catalyst. The experimental results show that under the conditions of Al/Ni molar ratio 500, reaction pressure 0.5 MPA, reaction time 30 min and reaction temperature 25 鈩，
本文编号：2357880
[Abstract]:In this paper, a series of hyperbranched polyamide-amine macromolecules were synthesized by Schiff base reaction with 3-methylsalicylaldehyde, 3- tert-Ding Ji salicylaldehyde and 3-methoxy salicylaldehyde, respectively, using dodecylamine as branching chain to synthesize a series of hyperbranched substituted salicylaldehyde ligands. Three kinds of hyperbranched substituted salicylaldehyde ligands were complexed with nickel chloride hexahydrate to obtain a series of hyperbranched substituted salicylic aldehydes nickel complexes. A series of hyperbranched substituted salicylaldehyde ligands and a series of hyperbranched substituted salicylaldehyde-nickel complexes were characterized by IR, UV, 1H-NMR and ESI-MS. The catalytic properties of a series of hyperbranched substituted salicylaldehyde-nickel complexes for ethylene oligomerization were investigated, and the influence of the substituent group effect of the hyperbranched substituted salicylaldehyde-nickel complexes on the catalytic performance was preliminarily investigated. The ethylene oligomerization of hyperbranched substituted salicylaldehyde-nickel catalyst was investigated with toluene as solvent and methyl aluminoxane (MAO), chlorodiethyl aluminum (DEAC), times hemiethyl aluminum chloride (EASC) as co-catalyst. The experimental results show that under the conditions of Al/Ni molar ratio 500, reaction pressure 0.5 MPA, reaction time 30 min and reaction temperature 25 鈩，
本文编号：2357880
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2357880.html
教材专著
