本文選題：膦磺酸鈀 + 鎳催化劑��； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年碩士論文

【摘要】：聚酯與聚烯烴是兩類應(yīng)用極其廣泛的聚合物,其生產(chǎn)工藝的改進(jìn)、聚合物性能的提高均具有十分重要的意義與價(jià)值。多年來(lái),眾多科研工作者投入到研發(fā)新型聚合反應(yīng)催化劑的工作中,在學(xué)術(shù)界與工業(yè)界均有所突破。自齊格勒-納塔催化劑問世以來(lái),通過(guò)對(duì)催化劑的調(diào)節(jié)來(lái)改進(jìn)烯烴聚合反應(yīng)的活性以及聚合物的性能已獲得了極大成功。然而,在烯烴與極性單體的共聚反應(yīng)中,極性單體中的部分官能團(tuán)對(duì)催化劑的毒化作用始終限制著絕大多數(shù)催化劑的實(shí)際應(yīng)用前景。研發(fā)擁有高官能團(tuán)容忍度的新型催化劑成為了我們工作的重點(diǎn)。在本篇論文中,我們通過(guò)對(duì)催化劑配體進(jìn)行修飾,引入第二層配位空間,以達(dá)到在極性單體存在情況下穩(wěn)定催化劑活性中心的作用,借此改進(jìn)開環(huán)聚合以及烯烴與極性單體共聚的性能。1.首先,我們合成并表征了一系列含有吡咯亞胺配體的鋁配合物,并對(duì)其催化己內(nèi)酯開環(huán)聚合的反應(yīng)性能進(jìn)行了分析。這些配合物的配體上含有由氧、硫等雜原子取代的官能團(tuán)邊臂。這些雜原子的引入,形成了第二層配位空間,它們可以在很大程度上提高配合物的催化活性。在實(shí)際催化反應(yīng)中,當(dāng)加入芐醇作為引發(fā)劑時(shí),這些配合物可以可控且高效地催化己內(nèi)酯的開環(huán)聚合;在沒有芐醇等引發(fā)劑存在的條件下,它們依舊保持著高活性和可控性。2.其次,我們合成并表征了一系列含有不同長(zhǎng)度烷氧鏈取代基的膦磺酸鈀、鎳配合物,并對(duì)其催化烯烴聚合的反應(yīng)性能進(jìn)行了分析。催化劑配體取代基上的聚乙二醇單元與金屬中心或極性單體的相互作用可以調(diào)節(jié)乙烯聚合和共聚過(guò)程。在乙烯聚合中,該策略導(dǎo)致活性提高、催化劑穩(wěn)定性提高和聚乙烯分子量增大。在乙烯與極性單體共聚反應(yīng)中,可以實(shí)現(xiàn)多種共聚參數(shù)的改進(jìn)(包括單體插入比、共聚物熔點(diǎn)等)。對(duì)于具有氫鍵供體能力的極性單體,這種效果最為顯著。
[Abstract]:Polyester and polyolefin are two kinds of polymers which are widely used. It is of great significance and value to improve the production process and properties of polymers. For many years, many researchers have devoted themselves to the research and development of new polymerization catalysts, and have made breakthroughs in both academia and industry. Since Ziegler-Natta catalyst came into being, the activity of olefin polymerization and the performance of polymer have been greatly improved by adjusting the catalyst. However, in the copolymerization of olefins and polar monomers, the toxicity of some functional groups in polar monomers has always restricted the practical application prospects of most of the catalysts. Research and development of new catalysts with high functional group tolerance has become the focus of our work. In this paper, we modify the catalyst ligands and introduce the second coordination space to stabilize the active centers in the presence of polar monomers. In order to improve the ring-opening polymerization and olefin and polar monomer copolymerization properties. 1. Firstly, a series of aluminum complexes containing pyrrolidine ligands were synthesized and characterized, and their catalytic properties for ring-opening polymerization of caprolactone were analyzed. The ligands of these complexes contain functional arm which is replaced by oxygen, sulfur and other heteratomic atoms. The introduction of these heteroatoms forms a second coordination space, which can improve the catalytic activity of the complexes to a great extent. In the actual catalytic reaction, when benzyl alcohol is added as initiator, these complexes can catalyze the ring-opening polymerization of caprolactone in a controllable and efficient manner, and they still maintain high activity and controllability in the absence of benzyl alcohol and other initiators. Secondly, a series of palladium and nickel phosphine sulfonate complexes with different alkoxy chain substituents were synthesized and characterized, and their catalytic properties of olefin polymerization were analyzed. The polymerization and copolymerization of ethylene can be regulated by the interaction of polyethylene glycol units with metal centers or polar monomers on the catalyst ligand substituents. In ethylene polymerization, this strategy leads to higher activity, higher catalyst stability and higher molecular weight of polyethylene. In the copolymerization of ethylene with polar monomers, a variety of copolymerization parameters (such as monomer insertion ratio, copolymer melting point, etc.) can be improved. This effect is most remarkable for polar monomers with hydrogen bond donor ability.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;O631.5

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