金屬催化劑和有機催化劑被廣泛用于烯烴聚合以及開環(huán)聚合中。本論文分為四個主要部分。1.研究了樟腦基膦-羰基配體在鎳催化的乙烯齊聚反應中的應用。在本節(jié)中,我們合成并表征了含聯(lián)芳基的樟腦基膦-羰基配體及相應的Ni和Pd配合物。通過引入聯(lián)芳基結構,能夠產生Ni-芳基次級作用,增加聚合產物的分子量。樟腦骨架作為給電子基團,使膦和羰基配位基團更富電子。此外,樟腦骨架的剛性橋環(huán)結構可有效抑制PC-CO鍵的旋轉,從而有利于提高聚合產物的分子量。2.研究了一系列帶有不同含氮第二層配位空間基團的水楊醛亞胺配體,將其應用于鋅和鋁配合物催化的開環(huán)聚合,并研究了上述鋅和鋁配合物催化的外消旋丙交酯的開環(huán)聚合中的立體選擇性,以及鋁催化劑在外消旋丙交酯與戊內酯和己內酯單體共聚時的選擇性。在室溫或低溫條件下,具有3-位大位阻三苯基甲硅烷基的鋅催化劑配合物可催化外消旋丙交酯的立體選擇性開環(huán)聚合,產生高度雜同立構的聚乳酸。此外,使用上述鋁催化劑能夠在高溫條件下催化外消旋丙交酯的均聚及其與戊內酯和己內酯單體的無規(guī)共聚。3.研究了一系列α-酮亞胺類鎳催化劑催化乙烯聚合,產生高分子量的帶有支鏈的聚乙烯該催化劑容易合成,且具有靈活... 

【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)】：166 頁

【學位級別】：博士

【文章目錄】：
摘要
abstract
Chapter one 1 Introduction and fundamental concepts
    1.1 Polyolefins
    1.2 Olefins polymerization
    1.3 Catalysts for olefin polymerization
        1.3.1 Chain walking polymerization
        1.3.2 The effects of ligand-substrate
        1.3.3 Metal-substrate effect
    1.4 Ring opening polymerization
        1.4.1 Radical ring opening polymerization (RROP)
        1.4.2 Cationic ring opening polymerization (CROP)
        1.4.3 Anionic ring opening polymerization (AROP)
        1.4.4 Ring opening metathesis polymerization (ROMP)
    1.5 Thesis overview
    1.6 References
Chapter two 2 Camphor-based phosphine-carbonyl ligands for Ni catalyzed ethylene oligomerization
    2.1 Introduction
    2.2 Results and discussions
    2.3 Experimental
        2.3.1 Preparation of Ligand L1
        2.3.2 Preparation of Ligand L2
        2.3.3 Preparation of Pd1
        2.3.4 Preparation of Ni1
        2.3.5 Preparation of Ni2
        2.3.6 Oligomerizadon Procedure, General Procedure for the Ni1-Catalyzed oligomerization
        2.3.7 Oligomerizadon Procedure, General Procedure for the Ni2-Catalyzed oligomerization
    2.4 Conclusions
    2.5 References
Chapter three 3 Phenoxyimine ligands bearing nitrogen-containing second coordination spheres for zinccatalyzed stereoselective ring-opening polymerization of rac-lactide
    3.1 Introduction
    3.2 Results and discussions
        3.2.1 Synthesis and Characterization of Complexes Zn1-Zn6 and A16
        3.2.2 Zn catalyzed ROP
    3.3 Conclusion
    3.4 Experimental section
        3.4.1 General
        3.4.2 Copolymerization of rac-LA and CL/VL catalyzed by A16
        3.4.3 Polymerizations
    3.5 References
Chapter four 4 Synthesis and characterization of a-imino-ketone nickel platforms for polymerization ofhigh molecular weight polyolefms
    4.1 Introduction
    4.2 Synthesis and Characterization of the Nickel Complexes
        4.2.1 Synthesis of ligands and catalysts
    4.3 Conclusion
    4.4 References
Chapter five 5 Lewis acid/base modulation on sidearm group in (thio)urea/alkoxide mediated switchablering-opening polymerization of cyclic esters
    5.1 Introduction
    5.2 Experimental
        5.2.1 Materials
        5.2.2 Instrumentation
        5.2.3 Synthesis of Ureas Bearing Pyridyl Group
        5.2.4 Synthesis of Thioureas Bearing Pyridyl Group
    5.3 General Procedure for Ring-opening Polymerization
    5.4 Results and Discussion
    5.5 Conclusions
    5.6 References
Appendix A Camphor-based phosphine-carbonyl ligands for Ni catalyzed ethylene oligomerization
    NMR and ESI-MS spectra of ligands and catalysts
    MALDI-TOF-MS resuts of catalysts
    DSC results of ethylene oligomers
    GPC results of ethylene oligomers
    GC and GC-MS results of ethylene oligomers
    X-ray Crystallography
Appendix B Phenoxyimine ligands bearing nitrogen-containing second coordination spheres for zinccatalyzed stereoselective ring-opening polymerization of rac-lactide
    ~1H NMR and ~(13)C NMR of the ligands and zinc complexes
        ~1H NMR and ~(13)C NMR of the materials
        ~1H NMR and ~(13)C NMR of the ligands (L1-L6)
        ~1H NMR and ~(13)C NMR of the complexes (Zn1-Zn6, A16)
    MALDI-TOF MS of the polymers
    X-ray structure determination
Appendix C Synthesis and characterization of α-imino-ketone nickel platforms for polymerization of highmolecular weight polyolefins
    ~1H NMR and ~(13)C NMR of the ligands and metal complexes
    ESI-MS of ligands
Appendix D Lewis acid/base modulation on sidearm group in (thio) urea/alkoxide mediated switchablering-opening polymerization of cyclic esters
    NMR and HRMS results of ligands and catalysts
    Molecular packing of 2-O
    Crystal Data and Structure Refinement for 2-O
    Fractional Atomic Coordinates
    Anisotropic Displacement Parameters
    Bond Lengths for 2-O
    Bond Angles for 2-O
    Hydrogen Atom Coordinates
Publications


【參考文獻】：
期刊論文
[1]Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones[J]. Zhuo-Lun Jiang,Jun-Peng Zhao,Guang-Zhao Zhang.  Chinese Journal of Polymer Science. 2019(12)
[2]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)
[3]Lewis acid/base modulation in β-diiminate zinc-catalyzed switchable ring-opening polymerization of rac-lactide[J]. Pan Zhang,Minhui Zhao,Wenmin Pang,Changle Chen.  Science China（Chemistry）. 2019(04)
[4]Synthesis of silicon-functionalized polyolefins by subsequent cobalt-catalyzed dehydrogenative silylation and nickel-catalyzed copolymerization[J]. Shixin Zhou,Changle Chen.  Science Bulletin. 2018(07)



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