Synthesis Of Rosin Based Gemini Surfactants And Preparation Of Nanometer Materials

In this paper, we have prepared four types of Gemini surfactant using rosin as raw materials, and discussed preliminarily the methods and properties of nanometer and mesoporous materials which were prepared by using rosin derivatives based surfactants as templates. This thesis is mainly divided into two parts.The first part concerned the preparation and analysis of the rosin derivative Gemini surfactants and the results are as follows:(1)We prepared tetramethylethylenediamine-bis rosin based Gemini surfactant I using rosin, epichlorohydrin and bisethane as raw materials and then identified its chemical structure with FTIR analysis. The optimal condition of synthesizing objective product can be determined by single-factor experiments and it can be described as follows:molar ratio is2.2:1, temperature is85℃and time is20h. The product owns the yield of76.70%and purity of96.10%.(2)We utilized rosin and dehydrogenated rosin respectively to react with N,N,N',N'-Tetramethyl-1,3-propanediamine which was used as connection group and prepared the N,N,N',N'-Tetramethyl-1,3-propanediamine-bis rosin based Gemini surfactant Ⅱ with the yield of70.5%and purity of95.5%and N,N,N',N'-Tetramethyl-1,3-propanediamine-bis dehydroabietyl Gemini surfactant Ⅲ with the yield of71.0%and purity of95.9%, respectively.(3)We synthesized ethylenediamine-bis abietinylglycine Gemini surfactant IV and ethylenediamine-bis dehydroabietyl Gemini surfactant by the use of acyl chloride, amidation and salifying chemical synthesis methods with rosin and dehydroabietic acid as raw material, respectively. Then, the chemical structure of the objective products was confirmed by FTIR and1H-NMR analysis.(4)The surface activity analysis results of the four Gemini surfactants shows that the CMC of Ⅰ,Ⅱ,Ⅲ and Ⅳ are1.42×10-4,4×10-4,6×10-4and5×10-4mol/L, the γcmc are36.69mN·m-1,37.35mN·m-1,36.63mN·m-1and34.208mN m-1, the pc20are4.15,4.43,4.45and3.81and the emulsification time are16min,20min,25min and2.5h, respectively. Ⅰ,Ⅱ and Ⅲ have good miscibility with anion, while Ⅳ has good miscibility with anion and cation.The second part is about the preparation and analysis of nanometer (mesoporous) materials and the results are as follows:(1) We prepared three types of nanometer TiO2particles:Tio(without surfactant), Ti0.5(adding0.5g surfactant) and Ti1.0(adding1.0g surfactant) using tetrabutyl titanate as raw materials and ethylenediamine-bis dehydroabietyl Gemini surfactant as templates via hydrothermal synthesis method. The XRD, SEM and TEM results analysis shows that three are all anatase structure, the dispersing effect of Ti1.0particles is better than Ti0and Ti0.5and there is no obvious aggregation among them, and the size of which is about8.81nm. The result of the photocatalytic degradation RhB shows that the photocatalytic activity of Ti1.0is better than Tio and Ti0.5and the degradation rate is99.7%for3hours' reaction, almost decomposed completely.(2) Preparation of two kinds of SiO2particles:①Nanosized SiO2was prepared using Gemini surfactant Ⅳ as template and tetraethyl silicate as raw material via sol-gel method. Analyzed by TEM and XRD, SiO2is kind of porous material constituting by nanometer particles and which corresponds to amorphous structure. Through the nitrogen adsorption-desorption experiment, we can get that the specific surface area, cumulative pore volume and average pore diameter of SiO2is116.83m2/g,0.45cm3/g and15.31nm, respectively.②Preparation of mesoporous SiO2material with Gemini surfactant Ⅱ as templates and tetraethyl silicate as raw material by microemulsion method. It is a kind of mesoporous material and corresponds to amorphous structure, and which is made up with nanometer particles analyzed by TEM and XRD. Through the nitrogen adsorption-desorption experiment, we can get that the specific surface area, cumulative pore volume and average pore diameter of SiO2is928.10m2/g,1.04cm3/g and4.49nm, respectively.(3) Preparation of two kinds of calcium carbonate particles:①We prepared hydrophobic calcium carbonate particles using disodium sulfodehydroabietate served as templates, sodium carbonate and calcium chloride as raw material and oleic acid as organic matter. Through the analysis of TEM results, we can see that the calcium carbonate is a kind of nanorod structure whose average particle diameter is64.4nm. XRD result analysis shows that it is calcite structure. Besides, FTIR analysis proves that the calcium carbonate particles have been successful modified by organic acid and whose water contact angle is117.49°.②Preparation of hydrophobic calcium carbonate using sulfodehydroabietic acid based monosodium as template and oleic acid as organic matter. Through the analysis of SEM and TEM results shows that the product is hollow sphere made up with nanometer particles, the spherical diameter ranges from2to3μm and the hollow size is less than1μm. The XRD result analysis shows that it is the mixed crystal of aragonite and calcite and the mole content are81.1%and8.9%, respectively. FTIR and TG results analysis proves that the calcium carbonate particles have been successful modified by organic acid oleic acid and whose water contact angle is95°. Two kinds of calcium carbonate particles have reached to hydrophobic property.