The development of novel polymerization routes towards functional polymers is always of great importance to polymer chemists and material scientists. Among the numerous monomers, those containing carbon-carbon triple bonds serve as versatile monomers for the construction of functional polymers with various constructing units, including triple bonds, double bonds, aromatic rings, fused rings and heterocycles, etc. In this program, I intended to develop a series of new synthetic methodologies for acetylenic polymers based on efficient organic reactions from terminal or internal alkynes as the monomers. Most of the polymers contain luminogens with aggregation-induced emission characteristics (AIEgens) in their structures, and exhibit interesting photophysical properties.

Chapter 1 gives...[ Read more ]

The development of novel polymerization routes towards functional polymers is always of great importance to polymer chemists and material scientists. Among the numerous monomers, those containing carbon-carbon triple bonds serve as versatile monomers for the construction of functional polymers with various constructing units, including triple bonds, double bonds, aromatic rings, fused rings and heterocycles, etc. In this program, I intended to develop a series of new synthetic methodologies for acetylenic polymers based on efficient organic reactions from terminal or internal alkynes as the monomers. Most of the polymers contain luminogens with aggregation-induced emission characteristics (AIEgens) in their structures, and exhibit interesting photophysical properties.

Chapter 1 gives a brief introduction to the definition of acetylenic polymers. Their synthesis methodologies are typed into three categories based on the components: homo-polymerization, two-component polyannulation and multi-component polymerization. Some symbolic properties and functionalities of the polymers are exhibited with examples. This chapter also mentions remained problems and raises the perspectives in this research field. Finally, the thesis objective and research strategies of my PhD study is summarized.

Chapters 2-7 are related to the development of new polymerization methods and investigation on the properties and applications of the generated polymers. Chapters 2 and 3 discuss three-component polymerizations of alkynes to generate poly(dipropargyl amine)s and poly(tetraphenyl ethene)s, respectively, while two-component polyannulation or polycoupling reactions are investigated in Chapters 4-7. Polymerizations in Chapters 2 and 7 utilize terminal alkynes as monomers, while internal diynes are used in Chapters 3-6. Polymers generated in this thesis program have the skeletons containing carbon-carbon triple bonds (Chapter 2), C=C double bonds (Chapters 3 and 6), benzene rings (Chapter 7) or fused heterocyclic rings (Chapters 4-5). Also, some polymers are endowed with AIE features by in situ generation of AIEgens in their structures (Chapters 3 and 6), and the rest are incorporated with chromophores via proper design of the monomers structures.

In each chapter, a research background of the project is introduced first, and then experimental details of the polymerization and the process of condition optimization are described. IR and NMR spectroscopies are utilized to characterize the structures of the polymers, and usually model reactions are conducted for comparison or mechanism study. The optical properties of the optical-active polymers are investigated by UV and PL spectroscopy in solution, aggregate or solid state. Preparation of polymer films allows the following study of their refractivity and photopatterning capability. Some other properties, such as thermal stability and solubility are also tested in order to explore their potentials in many real-world applications. Besides, some interesting functionalities, such as quantitative detection of explosives and metal ions, sensing volatile organic compounds and mechanic forces are investigated according to their respective performance.