含杂环苯并咪唑和苯并恶唑的高性能聚酰亚胺的合成和性能研究

发布时间：2020-12-04 19:35

　　芳香族聚酰亚胺是一类高性能的高分子材料,由于其具有优异的热、电、机械稳定性和良好的耐化学性能,在航空航天、微电子等领域有着重要的应用。然而,为了满足高性能材料在航空航天和电子工业中日益增长的需求,需要生产出能长时间忍受高温的易加工低成本的聚酰亚胺树脂。同样作为高性能杂环聚合物的苯并唑类聚合物,特别是聚苯并咪唑和聚苯恶唑,由于其优异的力学性能、热及氧化稳定性,也引起了人们广泛的研究兴趣。然而,这些杂环聚合物的主要缺点是由于它们的刚性骨架结构、不溶不熔而导致的苛刻的加工条件。单体或聚合物结构改性调控被认为是性能优化平衡的有效途径。因此,本论文研究基于酰亚胺和苯并唑类单元（即苯并咪唑、苯并恶唑）的共聚物,旨在整合其优异的力学、热学性能以及提高其加工性能。（1）通过改变刚性的2-（4-氨基苯基）-5-氨基苯并咪唑（BIA）和柔性的4,4’-二氨基二苯醚（ODA）,采用一步法制备了两个系列的基于3,3’三苯二醚二酐（3,3’-HQ DPA）的封端的聚酰亚胺均聚物和共聚物,以扩大可熔融加工的聚酰亚胺的工作温度范围。研究结果发现聚合物具有优异的性能:如良好的溶解性,高的玻璃化转变温度（Tg=354-... 

【文章来源】：中国科学院大学(中国科学院宁波材料技术与工程研究所)浙江省

【文章页数】：147 页

【学位级别】：博士

【文章目录】：
摘要
ABSTRACT
CHAPTER 1:Theoretical background
    1.1 Polyimides
    1.2 Synthetic methods and mechanisms
        1.2.1.Two-step polycondensation
            1.2.1.1 Thermal imidization of poly（amic acid）s
            1.2.1.2 Chemical imidization of poly（amic acid）s
        1.2.2.High temperature one-step polycondensation
        1.2.3.Polyimides via aromatic nucleophilic substitution polymerization
    1.3 Structural modifications to improve properties of polyimides
        1.3.1.Polyimides with flexible ether linkages
        1.3.2.Asymmetric polyimides
        1.3.3.Isomeric polyimides
    1.4 Polybenzazoles
        1.4.1.Polybenzimidazole
            1.4.1.1 Historical background of PBI
            1.4.1.2 Synthetic methods
            1.4.1.3 Structural modifications
                Poly （arylene ether benzimidazole） by SNAr
                Polybenzimidazole-polyimides
        1.4.2.Polybenzoxazole
            1.5.1.1 Synthetic methods
            1.5.1.2 Structural modifications
                Poly（aryl ether-benzoxazoles）by SNAr
                Polybenzoxazole polyimide
    1.5 Research strategy,objectives and its significance
CHAPTER 2:Materials and experimental instrumentatin
    2.1 Materials
        2.1.1 Diamines and （di） anhydrides
        2.1.2 Solvents
        2.1.3 Other reactants
    2.2 Instrumentation
        2.2.1.Physical properties （melting point, viscosity and solubility） measurements
        2.2.2.NMR spectroscopy
        2.2.3.Fourier transform infrared spectra（FT-IR）
        2.2.4.Gas chromatography mass spectrometry （GC-MS）
        2.2.5.Ground state geometry
        2.2.6.TGA/DSC
        2.2.7.Tensile properties measurements
        2.2.8.UV-vis analysis
        2.2.9.Water uptake measurement
        2.2.10.Wide-angle X-ray diffraction
        2.2.11.Molten index instrument
        2.2.12.Rotational physical Rheometer
g, melt processable copolyimides based on isomeric 3,3" and="" 4,4'-hdroquinone="" diphthalic="" anhydride="" （hqdpa）'="">CHAPTER 3:High T_g, melt processable copolyimides based on isomeric 3,3'and 4,4'-hdroquinone diphthalic anhydride （HQDPA）
    3.1 Introduction
    3.2 Synthesis of polymers
    3.3 Results and discussion
        3.3.1.Synthesis and characterization
        3.3.2.Thermal properties
        3.3.3.Mechanical properties
        3.3.4.Dynamic mechanical properties
        3.3.5.Solubility
        3.3.6.Rhelogical Properties
            3.3.6.1 Melt flow index （MFI）
            3.3.6.2 Melt Processability
        3.3.7.Optical Properties
        3.3.8.Wide-angle X-ray diffraction
    3.4 Summary
CHAPTER 4:Processable, high Tg polyimide from unsymmetrical diamines containing 4-phenoxy aniline and benzimidazole moieties
    4.1 Introduction
    4.2 Synthesis of diamines and polymers
    4.3 Result and discussion
        4.3.1 Synthesis and characterization
        4.3.2 Thermal properties
        4.3.3 Dynamic mechanical properties
        4.3.4 Solubility
        4.3.5 Mechanical properties
        4.3.6 Wide-angle X-ray diffraction
        4.3.7 Controlled Mw polymers
    4.4 Summary
CHAPTER 5:Processable poly（benzoxazole imide）s derived from asymmetric benzoxazolediamines containing 4-phenoxy aniline:Synthesis,properties and isomeric effect
    5.1 Introduction
    5.2 Synthesis of monomers and polymers
    5.3 Results and discussion
        5.3.1.Synthesis and characteriaztion
        5.3.2.Phase transition
        5.3.3.Thermal properties
        5.3.4.Dynamic mechanical properties
        5.3.5.Solubility
        5.3.6.Mechanical properties
        5.3.7.UV-Vis
        5.3.8.Wide-angle X-ray diffraction
        5.3.9.Controlled Mw polymers
    5.4 Summary
g and organosoluble poly（N-arylene benzimidazole etherimide） copolymers by C-N/C-O coupling reaction">CHAPTER 6:Synthesis of high T_g and organosoluble poly（N-arylene benzimidazole etherimide） copolymers by C-N/C-O coupling reaction
    6.1 Introduction
    6.2 Synthesis of monomers and polymers
    6.3 Result and discussion
        6.3.1 Synthesis and characterization
        6.3.2 Solubility
        6.3.3 Thermal properties
        6.3.4 Mechanical properties
        6.3.5 Dynamic mechanical properties
        6.3.6 Water uptake
        6.3.7 Wide-angle X-ray diffraction
    6.4 Summary
CHAPTER 7:Conclusion and outlook
REFERENCES
PUBLICATION LIST
ACKNOWLEDGEMENTS


【参考文献】：
期刊论文
[1]Synthesis of a new pyridine-containing diamine and related polyimide[J]. Jiu Jiang Zhao,Chen Liang Gong,Shu Jiang Zhang,Yu Shao,Yan Feng Li~* State Key Laboratory of Applied Organic Chemistry,College of Chemistry and Chemical Engineering, Institute of Biochemical Engineering & Environmental Technology,Lanzhou University,Lanzhou 730000,China.  Chinese Chemical Letters. 2010(03)



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