新型镍/钯催化剂的合成及其在乙烯聚合及乙烯—极性单体共聚中的应用

发布时间：2021-07-23 06:34

　　自Zigler-Natta催化剂被发现以来,过渡金属催化的烯烃聚合在工业界和学术界受到了广泛的关注。20世纪90年代,Brookhart等人发现了具有良好极性官能团耐受性、能够催化烯烃与极性单体共聚的α-二亚胺钯催化剂,大大推动了后过渡金属催化的烯烃聚合领域的发展。该类催化剂具有独特的链行走机理,能够用于产生具有支化结构的聚烯烃材料。然而,早期的研究表明α-二亚胺Pd催化剂的热稳定性较低。在高温聚合的条件下,该类催化剂会迅速分解,导致聚合物分子量显著降低。为了改善α-二亚胺Pd催化剂的热稳定性,同时也为了调节聚烯烃产物的分子量和支化度,许多研究通过引入不同的取代基的方式,对配体进行空间位阻效应和电子效应进行调节,以期得到高性能的催化剂。例如,通过向配体结构中的苯胺部分或双酮骨架中引入具有较大空间位阻效应的取代基,能够抑制烯烃聚合中的链转移反应,从而实现高热稳定性和高分子量。此外,取代基电子效也对催化剂的热稳定性和聚合产物的分子量、支化度等等有显著地影响。本论文围绕后过渡金属催化的烯烃聚合开展了研究工作。本论文主要包括以下几个部分:1.在本论文第一章,对烯烃聚合中的α-二亚胺Pd催化剂进... 

【文章来源】：中国科学技术大学安徽省 211工程院校 985工程院校

【文章页数】：171 页

【学位级别】：博士

【文章目录】：
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


【参考文献】：
期刊论文
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