膦磺酸钯镍催化剂在烯烃与极性单体共聚反应中的应用

发布时间：2018-01-18 14:39

本文关键词：膦磺酸钯镍催化剂在烯烃与极性单体共聚反应中的应用　出处：《中国科学技术大学》2017年博士论文　论文类型：学位论文

【摘要】：自从齐格勒和纳塔发现烯烃聚合催化剂后,过渡金属催化的烯烃聚合在工业和学术界均取得了巨大成功。20世纪90年代Drent等人所报道的膦磺酸钯(醋酸钯)的催化剂对于单体与极性单体共聚领域是一个重大发现。自从这个催化剂问世以来,大量基于膦磺酸配体的钯,镍催化剂(尤其是钯催化剂)被广泛应用于乙烯聚合以及乙烯与多种极性单体的共聚。经过多年的研究,配体的调节方式多种多样。研究者设计了各种各样不同类型的功能性配体来进行催化剂的优化与调节。其中主要工作集中在对与P原子上取代基的调整变化。单是,通过P取代基的调节来得到新型高效的膦磺酸钯镍催化剂变得越来越难。因此在这篇论文中,我们尝试发展新的配体"平台"。通过对膦磺酸的基础构成骨架来进行改变,以求有所突破,改进经典膦磺酸配体催化剂常见的劣势(比如低分子量,低活性,低极性单体插入比等),并将其应用于乙烯与极性单体的共聚之中。1.首先,我们合成并表征以萘骨架为基础的新型膦磺酸配体。再以配体为基础,与适当的金属前驱物反应合成了相应的膦磺酸钯和镍的催化剂。并在不同条件下,进行了乙烯聚合和乙烯与极性单体共聚的研究。对比经典PO催化剂,骨架的变化引起了催化剂很大的性质变化,比如更高的聚合活性(10倍的活性提高),更高的聚合分子量,更高的热稳定性,以及更好的耐水性。同时,新的萘骨架催化剂在乙烯与MA共聚中表现优异,共聚物插入比可以高达40%。2.在找到一个新的高性能的萘催化剂后,我们继续研究这类PO催化剂体系的潜力。通过改变膦与磺酸基团的不同连接位置,来调控催化性质的性质。基于这一理念,我们合成并且表征了一系列催化剂,并且发现他们在乙烯聚合,以及乙烯-极性单体共聚和反应中表现出优异的性质。这提供了一种改善聚合催化剂性质的新研究方向。3.在萘环体系下,设计含有氧原子的官能团。并通过在配体中引入-OM(M为锂钠钾)基团,制备了一系列的金属催化剂。在聚合以及共聚过程中,碱金属离子,以及添加的不同的冠醚可以对催化剂性质产生影响。4.我们对膦磺酸催化剂改良研究进行了一些其他尝试,合成与表征。
[Abstract]:Since Ziegler and Natta discovered catalysts for olefin polymerization. Transition metal-catalyzed olefin polymerization has achieved great success in both industry and academia. Palladium phosphine sulfonate (palladium acetate) was reported by Drent et al in 90s of the 20th century. It is an important discovery in the field of monomer and polar monomer copolymerization. A large number of palladium and nickel catalysts (especially palladium catalysts) based on phosphine sulfonic acid ligands have been widely used in ethylene polymerization and copolymerization of ethylene with many polar monomers. The regulation of ligands is varied. The researchers designed various kinds of functional ligands to optimize and regulate the catalysts. The main work is to adjust the substituents to P atoms. Yes. It is becoming more and more difficult to obtain new and efficient phosphine sulfonate palladium nickel catalysts by adjusting the P substituents. We try to develop a new ligand "platform" by changing the basic framework of phosphine sulfonic acid in order to make a breakthrough and improve the common disadvantages (such as low molecular weight, low activity) of the classic phosphine sulfonic acid ligand catalyst. The low polar monomers were used in the copolymerization of ethylene and polar monomers. Firstly, we synthesized and characterized new phosphine sulfonic acid ligands based on naphthalene skeleton and then based on ligands. The corresponding catalysts of PD and Ni phosphine sulfonate were synthesized by reaction with appropriate metal precursors. The polymerization of ethylene and copolymerization of ethylene with polar monomers were studied under different conditions. The changes in the skeleton lead to a great change in the properties of the catalyst, such as higher polymerization activity 10 times higher activity, higher polymerization molecular weight, higher thermal stability, and better water resistance. The new naphthalene skeleton catalyst performed well in ethylene copolymerization with MA, and the intercalation ratio of the copolymer could be as high as 40. 2. After finding a new high performance naphthalene catalyst, a new naphthalene catalyst with high performance was found. We continue to study the potential of this type of PO catalyst system to regulate the catalytic properties by changing the different sites of phosphine and sulfonic groups. We synthesized and characterized a series of catalysts and found that they were polymerized in ethylene. And the excellent properties of ethylene-polar monomer copolymerization and reaction. This provides a new research direction to improve the properties of polymerization catalyst. 3. In naphthalene ring system. A series of metal catalysts were prepared by introducing the lithium-sodium potassium group into the ligands. In the process of polymerization and copolymerization, alkali metal ions were prepared. And the addition of different crown ethers can affect the properties of the catalyst. 4. We have made some other attempts, synthesis and characterization of phosphine sulfonic acid catalyst improvement.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36;O631.5

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