本文關(guān)鍵詞：膦磺酸鈀鎳催化劑在烯烴與極性單體共聚反應(yīng)中的應(yīng)用　出處：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 烯烴聚合 膦磺酸鈀及鎳 極性單體共聚 骨架變化 調(diào)節(jié)

【摘要】：自從齊格勒和納塔發(fā)現(xiàn)烯烴聚合催化劑后,過渡金屬催化的烯烴聚合在工業(yè)和學(xué)術(shù)界均取得了巨大成功。20世紀(jì)90年代Drent等人所報(bào)道的膦磺酸鈀(醋酸鈀)的催化劑對于單體與極性單體共聚領(lǐng)域是一個(gè)重大發(fā)現(xiàn)。自從這個(gè)催化劑問世以來,大量基于膦磺酸配體的鈀,鎳催化劑(尤其是鈀催化劑)被廣泛應(yīng)用于乙烯聚合以及乙烯與多種極性單體的共聚。經(jīng)過多年的研究,配體的調(diào)節(jié)方式多種多樣。研究者設(shè)計(jì)了各種各樣不同類型的功能性配體來進(jìn)行催化劑的優(yōu)化與調(diào)節(jié)。其中主要工作集中在對與P原子上取代基的調(diào)整變化。單是,通過P取代基的調(diào)節(jié)來得到新型高效的膦磺酸鈀鎳催化劑變得越來越難。因此在這篇論文中,我們嘗試發(fā)展新的配體"平臺"。通過對膦磺酸的基礎(chǔ)構(gòu)成骨架來進(jìn)行改變,以求有所突破,改進(jìn)經(jīng)典膦磺酸配體催化劑常見的劣勢(比如低分子量,低活性,低極性單體插入比等),并將其應(yīng)用于乙烯與極性單體的共聚之中。1.首先,我們合成并表征以萘骨架為基礎(chǔ)的新型膦磺酸配體。再以配體為基礎(chǔ),與適當(dāng)?shù)慕饘偾膀?qū)物反應(yīng)合成了相應(yīng)的膦磺酸鈀和鎳的催化劑。并在不同條件下,進(jìn)行了乙烯聚合和乙烯與極性單體共聚的研究。對比經(jīng)典PO催化劑,骨架的變化引起了催化劑很大的性質(zhì)變化,比如更高的聚合活性(10倍的活性提高),更高的聚合分子量,更高的熱穩(wěn)定性,以及更好的耐水性。同時(shí),新的萘骨架催化劑在乙烯與MA共聚中表現(xiàn)優(yōu)異,共聚物插入比可以高達(dá)40%。2.在找到一個(gè)新的高性能的萘催化劑后,我們繼續(xù)研究這類PO催化劑體系的潛力。通過改變膦與磺酸基團(tuán)的不同連接位置,來調(diào)控催化性質(zhì)的性質(zhì)�；谶@一理念,我們合成并且表征了一系列催化劑,并且發(fā)現(xiàn)他們在乙烯聚合,以及乙烯-極性單體共聚和反應(yīng)中表現(xiàn)出優(yōu)異的性質(zhì)。這提供了 一種改善聚合催化劑性質(zhì)的新研究方向。3.在萘環(huán)體系下,設(shè)計(jì)含有氧原子的官能團(tuán)。并通過在配體中引入-OM(M為鋰鈉鉀)基團(tuán),制備了一系列的金屬催化劑。在聚合以及共聚過程中,堿金屬離子,以及添加的不同的冠醚可以對催化劑性質(zhì)產(chǎn)生影響。4.我們對膦磺酸催化劑改良研究進(jìn)行了一些其他嘗試,合成與表征。
[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.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O631.5

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