本文選題：不對稱結(jié)構(gòu) + 鈦配合物(IV)��； 參考：《吉林大學(xué)》2017年碩士論文

【摘要】：聚烯烴是一類產(chǎn)量大、應(yīng)用多的高分子材料,由于原料豐富、價格低廉、容易加工成型、良好的機械性能和熱性能、抗腐蝕性能優(yōu)良等特點,國內(nèi)外已廣泛應(yīng)用于包裝、建筑材料、電氣元件等諸多行業(yè),而且世界各國對聚烯烴材料的需求將持續(xù)增長。催化劑決定著聚合物的形貌、結(jié)構(gòu)以及性能,因此聚烯烴材料的發(fā)展與催化劑的進步密不可分。聚烯烴工業(yè)不斷地發(fā)展,人們對于具有特殊性能聚烯烴產(chǎn)品需求也日益增加,因此對于具有優(yōu)異性能的催化劑的研究與開發(fā)仍然有極其重要的意義。本文利用對叔丁基苯酚為基本原料,設(shè)計合成了一類具有不對稱結(jié)構(gòu)的胺雙酚四齒配體L1H2-L6H2,對配體的結(jié)構(gòu)進行了1H NMR、13C NMR等表征。采用一鍋法高產(chǎn)率得到了紅色或深紅色鈦配合物C1-C6。通過1H NMR、13C NMR、元素分析對配合物進行了表征,X射線單晶衍射分析確認了配合物C3、C4和C5的結(jié)構(gòu),表明金屬中心具有六配位的配位結(jié)構(gòu)。在配體中,其中一個N原子上連有兩個甲基,另一個N'原子上連接了兩個不同的取代基,在配體與金屬發(fā)生反應(yīng)之后,氮原子與金屬中心形成配位鍵,O-則與金屬中心形成σ鍵,配合物在空間上呈現(xiàn)非對稱的結(jié)構(gòu)。本文最后一章研究了配合物C1-C6的對烯烴聚合反應(yīng)的催化活性。相同的聚合條件下,以MAO助催化劑,配合物C1-C6對乙烯聚合反應(yīng)表現(xiàn)出了較高的催化活性,最高為3640 kg PE(mol Ti)-1h-1,活性順序與配合物結(jié)構(gòu)中取代基R1、R2空間位阻大小的順序相同。最合適的Al/Ti為800,當Al/Ti為800時聚合產(chǎn)物分子量最高為C3,其Mw達到36.6×104 g mol-1;聚合物分子量分布中等至較窄,其PDI處于1-4之內(nèi)。當聚合溫度加熱到80℃時,催化劑仍有較高的催化活性表明催化劑具有良好的熱穩(wěn)定性;通過延長聚合時間,發(fā)現(xiàn)其具有較長的催化壽命。聚乙烯的DSC及高溫GPC表明得到的是線性聚乙烯。在MAO的作用下,研究了配合物C1-C6對乙烯與1-己烯共聚反應(yīng)的催化性質(zhì),相同條件下活性隨著取代基R1、R2的增大而降低,己烯插入率隨著取代基R1、R2的增大而降低。己烯的初始濃度也影響著聚合反應(yīng)和聚合產(chǎn)物的性質(zhì),當Chexene=0.75mol L-1時,催化劑活性最高,隨著己烯濃度的升高,共聚反應(yīng)活性逐漸降低,聚合產(chǎn)物的分子量逐漸降低。共聚物分子量Mw處于3-17×104 g mol-1間,分子量分布較窄,PDI處于2-3之間。
[Abstract]:Polyolefin is a kind of high molecular material with large output and many applications. It has been widely used in packaging at home and abroad because of its rich raw materials, low price, easy processing, good mechanical and thermal properties, excellent corrosion resistance and so on. Building materials, electrical components and other industries, and the world's demand for polyolefin materials will continue to grow. Catalysts determine the morphology, structure and properties of polymers, so the development of polyolefin materials is closely related to the progress of catalysts. With the continuous development of polyolefin industry and the increasing demand for polyolefin products with special properties, it is still of great significance for the research and development of catalysts with excellent performance. In this paper, an asymmetric tetradentate amine bisphenol ligand L1H2-L6H2 was designed and synthesized by using p-tert-tert Ding Ji phenol as the basic raw material. The structure of the ligand was characterized by 1H-NMR-13C NMR. The red or crimson titanium complexes C1-C6 were obtained by one-pot method. The complexes were characterized by elemental analysis by 1H NMR-13C NMRs and characterized by X-ray single crystal diffraction. The structures of the complexes C _ 3C _ 4 and C _ 5 were confirmed, indicating that the metal center has a six-coordination coordination structure. In the ligand, one N atom is connected with two methyl groups, the other N 'atom has two different substituents. After the ligand reacts with the metal, the nitrogen atom forms a coordination bond with the metal center and the O-forms a 蟽 bond with the metal center. The complexes exhibit asymmetric structures in space. In the last chapter, the catalytic activity of complex C1-C6 for olefin polymerization was studied. Under the same polymerization conditions, the coordination compound C1-C6 exhibited higher catalytic activity for ethylene polymerization under the same polymerization conditions with MAO co-catalyst, with the highest catalytic activity of 3640 kg PE(mol Ti-1h-1.The order of activity was the same as the order of steric resistance of the substituent R _ 1R _ 2 in the structure of the complex. The most suitable Al/Ti is 800. When Al/Ti is 800, the maximum molecular weight of the polymer product is C _ 3, and its MW is 36.6 脳 10 ~ 4 g mol ~ (-1). The molecular weight distribution of the polymer is moderate to narrow, and its PDI is within 1-4. When the polymerization temperature is heated to 80 鈩，

本文編號：1805456