Based On The Polymerizable Surfactant Organic - Inorganic Hybrid Materials Preparation

Polymerizable quaternary ammonium surfactants not only have the feature of the surfactant, but also contain unsaturated double bond or triple bond. It may lead to polymerization under certain conditions,.due to self-assembly property of surfactants. Additionally, polymerizable quaternary ammonium surfactants play an important role in orientationing the materials' structure.Because of surfactants' ionic-exchange, polymerizable quaternary ammonium surfactants are liable to introduce a functional counter-ion because of surfactants' polymerized properties. Polymerizable quaternary ammonium surfactants are easy to modify the materials through the polymerization reactions.These structural features with polymerizable surfactants can promote formating nano-materials possessing many unique structures, including the opening polymer network structure. Compared with conventional methods, such fine structure of the polymer particles with the novel properties of the inorganic/organic nano-structured materials can be obtained. Therefore, the polymerizable quaternary ammonium surfactants have many advantages in terms of functional modification of materials and synthesis of composite materials via self-assembly process. Ordered self-assembled surfactant will be assembled with the possibility of nano-size chemical reaction, and provide the role of template for the media, so it has been drawn more concern among scientists. Combined with current new standard for fuel emissions, there is a growing emphasis on biphasic catalysis reaction, Recently, the study of biphasic catalysis has attracted wide interest. Therefore, enhancement of biphasic catalysis and simplization of process in separation and recovery of the catalysts and products are still need to solve current problems. Based on polymerizable surfactants' special features and our previous works related to using H2O2 as oxidant in ultra-deep desulfurization of fuel oil, we use phosphotungstic acid with large volume, structural stability and catalytic characteristics, and through ion exchange reaction with polymerizable surfactant cations, which were prepared for organic/inorganic hybrid materials. After that,the desirably and controllably structural composite materials can be abtained by APDDAB and phosphotungstates with the original trigger polymerization. The results indicated that composite materials with regularly changed surface structure were prepared by adjusting the molar ratio between APDDAB and PWA, in order to formate the structure of composite materials.Hybrid materials we prepared have two characteristics:the catalyst can be recycled, and oxidation products can be easily separated after the catalysis reaction, which are long to solve the current dilemma.Based on the idea mentioned above, this research refers to three parts as follows:(1)Through quaternization reaction, the new-type polymerizable surfactant,3-(acryloylamino)propyl dodecyldimethyl ammonium bromide (APDDAB), was synthesized. Then organic/inorganic microspheres were obtained via ion exchange with phosphotungstates (PWA). The microspheres thus prepared were characterized by Fouier transform infrared spectroscopy (FT-IR), Scanning electron microscope(SEM),1HNMR, thermogravimetric analysis (TGA) and elemental analysis, respectively.The results indicated that in our experimental conditions, APDDAB-PWA composite microspheres with different mole ratio were spherical structure, better dispersion and these microspheres have smaller size.(2) With the original trigger polymerization, organic-inorganic hybrid materials with different molar ratio of PWA to APDDAB, and regularly changed surface structure were successfully obtained. The organic-inorganic hybrid materials were futher characterized by Fouier transform infrared spectroscopy (FT-IR), Scanning electron microscope(SEM),1H NMR, thermogravimetric analysis (TGA), Mercury Porosimeters, Fluorescence spectrometer and elemental analysis, respectively.The results indicated that the hybrid materials which we synthesized were polymer, and had regularly changeable surface structure, at the same time, showed a certain degree of pore structure. self-assembly of polymerizable surfactants which played an important role in the modification and structure-orientation of materials. These polymers' preparation processing is an important reference on other similar materials.(3) The catalytic performances of the poly(APDDAB-PWA) hybrid materials were systematically investigated by using dibenzothiophene (DBT) oxidized by H2O2 in decalin as a model system so that some key factors related to the catalytic performances of the composite microspheres were obtained. The feasibility and regularity of this hybrid material in the biphasic catalysis reaction were further discussed systematicly and detailedly.In the system using (P(PWA-APDDAB)) as microreactor, according to difference between dosages of PWA and APDDAB, the composite materials (P(PWA-APDDAB)) have different surface morphologies. The results indicated that the composite materials used as microreactor has efficient performence in ultra-deep desulfurization of fuel oil, no matter what molar ratioes of materials were used.Meanwhile, the microreactors with different surface morphology also affected DBT oxidation reaction; and proper experimental conditions should be further discussed.