【摘要】：本論文以十二胺為支鏈合成了超支化聚酰胺-胺大分子,再分別與3-甲基水楊醛、3-叔丁基水楊醛、3-甲氧基水楊醛進行席夫堿反應合成系列超支化取代水楊醛配體,三種超支化取代水楊醛配體分別與六水氯化鎳進行絡合,得到系列超支化取代水楊醛鎳配合物;采用紅外光譜、紫外光譜、核磁氫譜(1H-NMR)和電噴霧電離質(zhì)譜(ESI-MS)表征手段對系列超支化取代水楊醛配體和系列超支化取代水楊醛鎳配合物進行結構表征,并且考察了系列超支化取代水楊醛鎳配合物催化乙烯齊聚反應的性能,并初步探索超支化取代水楊醛鎳配合物的取代基效應對催化劑性能的影響。以甲苯為溶劑,分別以甲基鋁氧烷(MAO)、一氯二乙基鋁(DEAC)、倍半乙基氯化鋁(EASC)為助催化劑,考察超支化取代水楊醛鎳系催化劑的乙烯齊聚性能。實驗結果表明,在Al/Ni摩爾比為500、反應壓力為0.5MPa、反應時間為30min、反應溫度為25℃的聚合條件下,以MAO和DEAC為助催化劑時超支化鎳系催化劑的活性為104 g mol-1 h-1數(shù)量級、以EASC為助催化劑時的活性為106 g mol-1 h-1數(shù)量級,并且在EASC為助催化劑時產(chǎn)物中出現(xiàn)奇數(shù)碳產(chǎn)物。研究發(fā)現(xiàn),在三種助催化劑條件下,系列超支化取代水楊醛鎳配合物催化劑的活性和高碳烯烴選擇性順序由高到低為:超支化甲氧基水楊醛鎳配合物,超支化叔丁基水楊醛鎳配合物,超支化甲基水楊醛鎳配合物。為了深入研究超支化水楊醛鎳系催化劑的反應機理,定量分析超支化鎳系催化劑活性的調(diào)控因素,對超支化鎳系催化劑在乙烯齊聚反應中的行為進行了簡單的表觀反應動力學研究,采用最小二乘法進行線性回歸作圖,得到反應速率關于反應壓力、催化劑的濃度的表觀反應級數(shù),并且求得反應活化能,進而建立三種催化劑的表觀動力學方程。
[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，

本文編號：2357880