Synthesis, Structures And Properties Of Perylene Derivatives And Carboxyl Modified Polysiloxane

Because of its unique structure, polysiloxane exhibited special properties, such as excellent resistance to high and low temperature, hydrophobicity, better film formation, low surface tension, chemical and biological inertness and high gas permeability. All of these properties can not be instead by other polymer materials. Therefore, polysiloxane are widely used in aerospace, electronics, light industry, textile, machinery and medical treatment fileds. Nowaday, polydimethylsiloxane, as an important segment of polysiloxane, inspired many foucs on the modification study to develop new types of polysiloxane. All of these new types not only possess the wonderful properties, but also own much specific and unique performance. Thus, we devote ourselves to the research on the synthesis and application of new type of polysiloxane.In this dissertation, investigations have been carried out and focused on the synthesis, characterized and application of modified polysiloxane. The contents are as follows:1. The aminopropyl-block agent was synthesized by tetramethyldisiloxane and allylamine through hydrosilylation reaction. The allylamine was preprocessed before used to prevent the adverse reaction. The amine-terminated polysiloxane has been synthesized by ring-opening polymerization with octamethylcycoltetrasiloxane (D4) and aminopropyl-block agent at110℃. The structure of amine-terminated polysiloxane was characterized by IR and1H NMR, and would be used in the succeeding activities.2. A novel kind of carboxyl and amide terminated polysiloxane was successfully synthesized from amine-terminated polysiloxane and succinic anhydride. The product was characterized by the1H NMR and13C NMR. Two lanthanide ions (Eu3+and Tb3+) were chosen to coordinate with CTP to obtain the luminescent polysiloxane materials with excellent fluorescence property (CTP-Ln, Ln=Tb or Eu). When products were irradiated by ultraviolet light, narrow-width red and green emissions were observed, which indicates the successful coordination and the existence of the intra-molecular energy transfer process. In order to investigate the coordination number and structure of CTP-Ln, the carboxyl-functionalized dimethylsiloxane (CFD) and the luminescent dimethylsiloxane-lanthanide ions materials (CFD-Ln) with the similar coordination environment were synthesized and the structure was confirmed by FT-IR, Fluorescence and XPS analysis. Through the qualities comparison between the CFD-Ln and CTP-Ln, the coordination structure of the CTP-Ln was clearly confirmed.3.(1) Perylene end capping polysiloxane (PECP), was successfully synthesized by reaction of amine-terminated polysiloxane and3,4,9,10-perylene tetracarboxylic dianhydride, and was characterized by FT-IR and1H NMR. Because of PECP exhibited orange emission under UV light, it could be used to dope with blue emission compound to obtain a series of different colors. Due to the absorption spectrum of PECP showed good overlap with the fluorescence emission spectrum of Bis (7,10-Bis-phenyl-fluoranthene) methylphenylsilane (BFMPS), which is indispensable for the occurrence of energy transfer in the doping systems. When the molar ratio of BFMPS/PECP reached1:1.6in dichloromethane, white light was achieved with CIE color coordinate (0.33,0.33). Though the CIE color coordinate of the solid state doping system had shift, the system was also locked at white light region.(2) With the same synthesis mechanism, perylene-containing polysiloxane (PCTP) was synthesized and characterized. The thermal analysis and fluorescence of the PCTP indicates that the modified polysiloxane has outstanding thermal stability and good fluorescence property. Due to the appearance of lone-pair electrons and better film formation, it could be self-assembled on iron surface and thus used in the corrosion protection area. EIS (electrochemical impedance spectroscopy) and SEM (scanning electron microscopy) results indicated the films could protect the iron from corrosion efficiently. In order to prove the important role of π-π interaction, perylene containing silane coupling reagent was also synthesized. It can be hydrolytic condensation in acid solution to product perylene groups in side chain. The comparison demonstrated that perylene containing silane coupling reagent had better corrosion prevention effect.4. Perylene derivative-modified polysiloxane was designed and synthesized through the amidation reaction between aminopropyl-terminal polysiloxane and perylene tetracarboxylic diester monoimides with n-dodecyl as the alkyl chain connected to the perylene core. The synthesized compound was subjected to IR and1H NMR. UV-vis, Fluorescence and thermal analysis revealed the compound had outstanding optical property and thermal stability. The liquid-crystalline property of the modified perylene derivative was characterized via differential scanning calorimetry, polarization optical microscope, X-ray powder diffraction, and small-angle X-ray scattering for the existing of π-π stacking. The regular morphology of the compound was evaluated via scanning electron microscopy and atomic force microscopy in tapping mode. The static contact angle of the perylene derivative with distilled water as the test liquid was112°. All the measurements revealed that the polysiloxane-modified perylene derivative exhibited good thermal stability, excellent optical property, good hydrophobic property, and low temperature liquid-crystalline property.