烯烃聚合和开环聚合中的金属及有机催化剂
发布时间：2021-06-11 12:35
金属催化剂和有机催化剂被广泛用于烯烃聚合以及开环聚合中。本论文分为四个主要部分。1.研究了樟脑基膦-羰基配体在镍催化的乙烯齐聚反应中的应用。在本节中,我们合成并表征了含联芳基的樟脑基膦-羰基配体及相应的Ni和Pd配合物。通过引入联芳基结构,能够产生Ni-芳基次级作用,增加聚合产物的分子量。樟脑骨架作为给电子基团,使膦和羰基配位基团更富电子。此外,樟脑骨架的刚性桥环结构可有效抑制PC-CO键的旋转,从而有利于提高聚合产物的分子量。2.研究了一系列带有不同含氮第二层配位空间基团的水杨醛亚胺配体,将其应用于锌和铝配合物催化的开环聚合,并研究了上述锌和铝配合物催化的外消旋丙交酯的开环聚合中的立体选择性,以及铝催化剂在外消旋丙交酯与戊内酯和己内酯单体共聚时的选择性。在室温或低温条件下,具有3-位大位阻三苯基甲硅烷基的锌催化剂配合物可催化外消旋丙交酯的立体选择性开环聚合,产生高度杂同立构的聚乳酸。此外,使用上述铝催化剂能够在高温条件下催化外消旋丙交酯的均聚及其与戊内酯和己内酯单体的无规共聚。3.研究了一系列α-酮亚胺类镍催化剂催化乙烯聚合,产生高分子量的带有支链的聚乙烯该催化剂容易合成,且具有灵活...
【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】：166 页
【学位级别】：博士
【文章目录】：
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
【参考文献】：
期刊论文
[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)
本文编号：3224546
【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】：166 页
【学位级别】：博士
【文章目录】：
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
【参考文献】：
期刊论文
[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)
本文编号：3224546
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