自Zigler-Natta催化劑被發(fā)現(xiàn)以來,過渡金屬催化的烯烴聚合在工業(yè)界和學術界受到了廣泛的關注。20世紀90年代,Brookhart等人發(fā)現(xiàn)了具有良好極性官能團耐受性、能夠催化烯烴與極性單體共聚的α-二亞胺鈀催化劑,大大推動了后過渡金屬催化的烯烴聚合領域的發(fā)展。該類催化劑具有獨特的鏈行走機理,能夠用于產(chǎn)生具有支化結構的聚烯烴材料。然而,早期的研究表明α-二亞胺Pd催化劑的熱穩(wěn)定性較低。在高溫聚合的條件下,該類催化劑會迅速分解,導致聚合物分子量顯著降低。為了改善α-二亞胺Pd催化劑的熱穩(wěn)定性,同時也為了調(diào)節(jié)聚烯烴產(chǎn)物的分子量和支化度,許多研究通過引入不同的取代基的方式,對配體進行空間位阻效應和電子效應進行調(diào)節(jié),以期得到高性能的催化劑。例如,通過向配體結構中的苯胺部分或雙酮骨架中引入具有較大空間位阻效應的取代基,能夠抑制烯烴聚合中的鏈轉移反應,從而實現(xiàn)高熱穩(wěn)定性和高分子量。此外,取代基電子效也對催化劑的熱穩(wěn)定性和聚合產(chǎn)物的分子量、支化度等等有顯著地影響。本論文圍繞后過渡金屬催化的烯烴聚合開展了研究工作。本論文主要包括以下幾個部分:1.在本論文第一章,對烯烴聚合中的α-二亞胺Pd催化劑進... 

【文章來源】：中國科學技術大學安徽省 211工程院校 985工程院校

【文章頁數(shù)】：171 頁

【學位級別】：博士

【文章目錄】：
摘要
ABSTRACT
Chapter 1. Introduction
    1.1 A brief historic overview of early and late transition metal catalysts
    1.2 Chain Walking Mechanism
    1.3 Steric tuning and its effects on polymerization
        1.3.1 Steric bulk of aromatic amines
        1.3.2 Steric bulk of backbone
    1.4 Electronic tuning and its effects on polymerization
        1.4.1 Electronic effect of ligand constitutional amines
        1.4.2 Electronic effect of ligand backbone
    References
Chapter 2. Concerted steric and electronic effects on α-diimine nickel-andpalladium-catalyzed ethylene polymerization and copolymerization
    2.1 Introduction
    2.2 Experimental
        2.2.1 Experimental instruments, reagents and materials
        2.2.2 Procedure for the Synthesis of 2,6-Dibenzhydryl substituted aniline 1 and 2
        2.2.3 Procedure for the Synthesis of Ligands 3 and 4
        2.2.4 Procedure for the Synthesis of Nickel Complexes Ni-3OMe and Ni-3F
        2.2.5 Procedure for the Synthesis of Palladium Complexes Pd-3OMe and Pd-3F
    2.3 Polymerization procedures
        2.3.1 General in-Situ-Activated Polymerization Procedure using Palladium and Nickelcatalysts
        2.3.2 General in-Situ-Activated Copolymerization Procedure using Palladium Catalysts
    2.4 Results and Discussion
        2.4.1 Synthesis and Characterization of Anilines, Ligands, and Their Metal Complexes
        2.4.2 Polymerization study of catalysts
        2.4.3 Ethylene Polymerization with Nickel Catalysts
        2.4.4 Ethylene Polymerization and Copolymerization with Palladium Catalysts
    2.5 Conclusions
    References
Chapter 3. Ortho-functionalized dibenzhydryl substituents in a-diimine Pd catalyzedethylene polymerization and copolymerization
    3.1 Introduction
    3.2 Experimental
        3.2.1 Experimental instruments, reagents and materials
    3.3 Preparation of 1a and 1b
        3.3.1 General procedure for the synthesis of 2 and 3
        3.3.2 General procedure for the synthesis of 4 and 5
        3.3.3 Procedure for the synthesis of 6
        3.3.4 Procedures for the syntheses of the ligands
        3.3.5 General procedure for the synthesis of the Pd catalysts
        3.3.6 General procedure for ethylene polymerization
        3.3.7 General procedure for Pd catalyzed ethylene copolymerization
    3.4 Results and discussion
        3.4.1 Ethylene homopolymerization by Palladium catalysts Pd1-Pd-4
        3.4.2 Ethylene Co-Polymerization n\by Palladium catalysts Pd1-Pd-4
    3.5 Conclusions
    References
Chapter 4. Ligand-metal secondary interaction effect in phosphine-sulfonate palladium andnickel catalyzed ethylene (co)polymerization
    4.1 Introduction
    4.2 Experimental
        4.2.1 Experimental instruments, reagents and materials
        4.2.2 Synthesis of ligands
        4.2.3 Synthesis of Catalysts
        4.2.4 Procedure for ethylene homopolymerization
        4.2.5 Procedure for copolymerization of ethylene with polar monomers
    4.3 Results and discussion
        4.3.1 Ethylene Homo-polymerization by palladium and nickel catalysts
        4.3.2 Ethylene Co-polymerization by palladium and Nickel catalysts
    4.4 Conclusions
    References
Summary and outlook
Acknowledgements
List of Publications


【參考文獻】：
期刊論文
[1]鎳催化劑用于超高分子量聚乙烯的制備（英文）[J]. 譚忱,陳昶樂.  Science Bulletin. 2020(14)
[2]α-二亞胺鎳和鈀催化的乙烯聚合及共聚反應中的位阻和電子協(xié)同效應（英文）[J]. Qasim Muhammad,譚忱,陳昶樂.  Science Bulletin. 2020(04)
[3]A Phenol-containing α-Diimine Ligand for Nickel-and Palladium-Catalyzed Ethylene Polymerization[J]. Chen Tan,Wen-Min Pang,Chang-Le Chen.  Chinese Journal of Polymer Science. 2019(10)
[4]Ni catalyzed ethylene copolymerization with polar monomers[J]. Igor E.Soshnikov,Changle Chen,Konstantin P.Bryliakov.  Science China（Chemistry）. 2019(06)
[5]Synthesis of silicon-functionalized polyolefins by subsequent cobalt-catalyzed dehydrogenative silylation and nickel-catalyzed copolymerization[J]. Shixin Zhou,Changle Chen.  Science Bulletin. 2018(07)
[6](a-Diimine)palladium catalyzed ethylene polymerization and （co）polymerization with polar comonomers[J]. Lihua Guo,Changle Chen.  Science China（Chemistry）. 2015(11)



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