Controllable Preparation And Properties Of Poly(Triazole)Materials Via "Click" Chemistry

In recent years,"click" chemistry has become an effective method to build functional monomers and polymers owing to its remarkable advantages, including high efficiency, regioselectivity, atom economy, high yield, easy product post-processing, insensitive to water and oxygen and environmentally friendly. Especially the polymers with1,2,3-triazole ring formed by copper(I)-catalyzed alkyne-azide click polymerizations afforded higher thermal stability. Hence, click chemistry reaction is very promising many fields, such as surface modification, preparation of optical, electric and biology functional materials, etc.In this paper, nine of monomers, fifteen kind of poly(triazole)s were prepared and their structure were characterized. The controllable preparation of poly(triazole)s based on "click" chemistry were investigated. The solubility of poly(triazole)s were improved by design of molecular structure, and the effect of monomer structure on the properties of poly(triazole)s were studies. The main contents of this dissertation include the following points:1. The research progress of functional poly(triazole)s was reviewed, and the concept, classify, development history of "click" chemistry were introduced.2. Three side-alkynes monomers and three side-azide monomers were designed and synthesized and their structures were characterized by FT-IR,’H-NMR. To study the controllable preparation of poly(triazole)s using high efficiency "click" chemistry, seven oligomers/poly(triazole)s were designed and synthesized by adding single-group monomer and tuning the feed ratio of two double-group monomers, respectively. Six poly(triazole)s with different main-chain structure were obtained. Their structures were analyzed in detail by FT-IR,1H-NMR spectra, the solubility and thermal stability of the polymer was researched.3. The effect of molecular average weight and chain structure on the solubility of poly(triazole)s were discussed, It is found that both introducing the flexible chain in backbone of poly(triazole)s and introducing substituted flexible side group on aromatic-ring of poly(triazole)s effectively improve the solubility of resultant polymers. Molecular weight of poly(triazole)s were measured by’H-NMR end-group analysis and static laser light scattering(SLLS) method, respectively. The results show that both adding single-group monomer and tuning the feed ratio of two double-group monomer can effectively accomplish the control polymerization of poly(triazole)s based on "click" chemistry, it pave the way for development and applied research of poly(triazole) materials. The morphology and thermal properties was measured by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA), the results prove that the poly(triazole)s are partially crystalline polymer and have good thermal stability. The1,2,3-triazole ring is beneficial to the improvement of thermal performance. Simultaneously, it is also that the poly(triazole)s with higer molecular weight shows better thermal properties.4. Three functional alkynes monomers with ultraviolet, visible and near-infrared absorption were designed and synthesized. By introducing alkyl chain diazides, two poly(triazole)s with broad band absorption was prepared by copper(I)-catalyzed alkyne-azide click polymerization. Their structures were characterized by FT-IR,’H-NMR, respectively. The properties of monomer and polymer were studies by UV-vis, DSC and TGA. The results show that it is possible to design and controllable prepare broad band absorption optical materials and the prepared poly(triazole)s have good solubility, thermal stability.