The Synthesis And Characterization Of Novel And Functionalized Silicone Materials Via "Click" Chemistry Reaction

With the development of science and technology,the development of material has changed quickly.Through "green chemistry",it is one of the research highlights to achieve hybrid materials and improve their performances.Click reaction is undoubtedly the first choice of functionalized novel material.The CuAAC reaction,as a classic reaction of Click reaction,has the advantages of fast reaction rate,mild reaction conditions,easy separation and purification of the product and high yields.Meanwhile,the 1,2,3-triazole ring in the product,as the characteristic structure of the product,provides an effective ligand for the later construction of new complexes and macromolecular cross-linking networks.In addition,the thiol-ene addition reaction,as one of the Click chemical reactions,has also attracted extensive attention.The thiol-ene reaction not only has the advantages of Click reaction,but also avoids using heavy metal catalyst,which is more environmentally friendly.Therefore,it is widely used in the fields of synthesis and modification of polymers,functional treatment of materials surface,preparations of nanomaterials,synthesis of biomedical materials and preparations of hydrogels.In recent years,reliable and accurate methods for explosive detection have been a hotspot topic of international concerns.Chemical explosive detection is critical to homeland security,environmental protection and military issues.With the increasement of social demand,more sensitive,more efficient and low-cost explosive detection methods have become the hottest topic of global anti-terrorism.Ionic liquids,as a kind of novel materials developed rapidly in recent years,have been applied from the initial catalysts and solvents to electrochemistry and gas absorption fields.Organosilicon materials have the advantages of excellent physiological inertia,excellent thermal stability and low temperature resistance,as well as good electrical insulation.As an important kind of organosilicon materials,POSS also has the above characteristics.Funcationalized ionic liquids with POSS could be better to improve the thermal stability of ionic liquid,expand the actual use temperature range,improve its gas adsorption,as well as gas adsorption and storage.In the meantime,based on the constructability and designability of ionic liquids,ILs based on POSS as a green solvent,is of great research significance and application value to be applied for explosive detection,In this paper,organosilicon compounds and organosilicon polymers,especially organosilicon ionic liquids and related elastomers are synthesized via Click chemical reaction in four aspects.1.Two new ionic liquids based on POSS structures were obtained from different POSS compounds through two synthetic pathways of thiol-ene reaction and quaternization reaction,respectively.Compared to the quaternization reaction,the reaction process of thiol-ene reaction,as the main method of preparing ionic liquid,is faster rate,higher yields,and easier to separate and extract from the mixture.The product obtained have been characterized by infrared spectrum,nuclear magnetic resonance spectrum(H spectrum and the C and Si spectrum),element analysis and high-resolution mass spectrometry,and thermogravimetric analysis and differential scanning calorimetry analysis.The data show that both ionic liquids have good thermal stability and low glass transition temperature,which are conducive to expand their application temperature ranges.Additionally,the unique amphiphilic nature of two ionic liquids prompted them to self-assemble into spherical vesicle structures in selective solvents.Furthermore,the fluorescence characteristics of both have made them have better detection performances for NP,DNP and PA.The results have shown that IL-POSS-Br has higher detection capability for picric acid than that of IL-POSS-Cl.In order to demonstrate the detection performance of ILs POSS for explosives more intuitively,a simple practical test is adopted to illustrate effectively that ionic liquids can be used as explosive sensors.2.Four novel ionic liquids based on POSS were synthesized via thiol-ene"Click" chemical reaction,two of which were imidazole functionalized ionic liquids based on POSS and two of which were pyridine functionalized ionic liquids based on POSS.These four ionic liquids also have excellent thermal stability and lower glass transition temperatures,which endowed them with a wider temperature range.Owing to these four ionic liquids have eight different functional ionic liquid chains,they have presented spherical vesicles with different diameters in the selective solvents.In the meanwhile,the differences between imidazole ring and pyridine ring also have corresponding influences on the self-assembly behaviors of ionic liquids,such as the differences of particle sizes and driving forces of vesicle structures formation.Fluorescence response performance tests results have shown that the four ionic liquids have obvious explosives detection ability,ionic liquids as green solvents,the detection ability has proved that ionic liquids could not only as basic compounds be used in catalysts,solvents sand electrochemistry,etc,but also be used as fluorescent sensors which are applied in picric acid and other explosives detections.These have promoted the development of ionic liquid applications and served the production,living and homeland security.3.Novel organosilicon fluorescent elastomers were synthesized from diene-imidazole ionic liquids and side-chain mercaptopropyl polysiloxane.In order to improve the strength and mechanical properties of the elastomers,octavinyl-POSS(OVP for short)was used as the reinforcing agent and crosslinking agent and added into the crosslinking system of ionic liquids.Ionic liquids are both catalysts and crosslinkers,therefore they have improved greatly the reaction process in order to the reaction of elastomers can be completed in just a few minutes.The imidazole rings not only provide fluorescent groups,but also serve as hydrogen bond donors for elastomer crosslinking.Furthermore,SEM was used to characterize elastomers,and it was found that the elastomers were transparent and uniformly dispersed without phase separation.In addition,POSS-Ln3+ compounds as modifiers were added into elastomer preparation processes,which could not only improve the thermal stability of elastomers,but also could improve the luminescent properties of elastomers.Thereby when the weightloss of elastomers modified are 5wt%,the temperature is above 500?,which was very excellent.4.Four compounds containing 1,2,3-triazole were synthesized via CuAAC reaction,and a new type of unreported needle crystal was formed based on C4 ligand and Ag+.Then the compounds and crystals were characterized and systematically analyzed by NMR,crystal analysis,UV absorption,fluorescence and TGA thermogravimetry.By comparing the UV and fluorescencent spectra of compounds containing silicon atoms and compounds without silicon atoms,it is proved that silicon atoms have certain influences on electrons transfer in these four compounds,but their effects are limited.Afterwards,by comparing the fluorescencent performances data of C4 and its corresponding complexes,it is shown that the Ag(I)complexes have excellent fluorescencent performances and have the potential to employed as fluorescent materials.