Preparation And Application Of Methoxy Functionalized Ordered Mesoporous Polymer Materials

In recent years, ordered mesoporous phenolic resin has received scientists’ widespread attention because it has a series of advantages, such as a large specific surface area, tunable pore size, alkali resistance, hydrophobicity and low cost. The modify of ordered mesoporous phenolic resin with functional groups, such as amino, carboxyl, thiol and hydroxyl and so on, can extend its application of physics, chemistry, biology, medicine, environment, materials. Among these, thiol(SH) functional materials have extensive uses. Firstly, thiol can interact with platinug, gold and ruthenium, especially well complexing gold nanoparticles. When thiol interacts with gold, it can be used for the preparation of spported gold catalyst, which can catalyze alkynes hydration reaction, silane hydrolysis reaction and so on. Secondly, thiol can used to remove heavy metal ion from waste water, especially for the "softness" high metal ions. Thirdly, thiol can also be oxidized into sulfonic group(SO3H), which can be prepared into acid catalyst catalyzing the esterification reaction, carbonyl addition reaction, etc.If the modify of MPs with thiol uses the method of physical mixing, it will cause a loss of activity. Similarly, if using post-synthesis, it will cause the blockage of channel by thiol existing in the channel. On the contrary, if we use the method of copolymerization, it can solve these problems such as the the blockage of channel and the loss of activity. In addtion to these, this method can enable thiol to exist in the skeleton stably. According to this train of thoughts, we study different catalyst’s catalytic activity in alkynes hydration reaction, silane hydrolysis reaction and esterification reaction of acetic acid with ethanol. We also study the thiol functional ordered mesoporous phenolic resin’s adsorptive property for heavy metal ions. The essay is mainly divided into the following three parts and the detailed descriptions are listed as follows:1. Firstly, using the method of solvent evaporation self-assembly(EISA) synthesis and the method of copolymerization, we prepared the highly ordered thiol functional mesoporous phenolic resin(SH-MPs), then through the redox reaction between the thiol and gold chloride acid in situ, we prepared the catalyst Au-SH/SO3H-MPs. On one hand, Au(III) be reduced to Au(0) by thiol and immobilized by thiol which is not be oxidized into SO3 H, solving the problem of the loss of Au NPs on rhe supported gold catalys. On the other hand, some thiol was oxidized into sulfonic group(SO3H), providing the acid site of the catalyst. Therefore, the catalyst is a kind of bifunctional catalysts, the Au NPs and SO3 H on the carrier can catalyze alkynes hydration reaction collectively and get fairly good yields. Besides, Au-SH/SO3H-MPs can also catalyze silane hydrolysis reaction excellently because its hydrophobicity.2. We use hydroxy thiophenol as raw materials, non-ionic surfactant F127 as template, formaldehyde as crosslinker preparing functional ordered mesoporous with high content of thiol materials(SH-MPs-H). On one hand, thiol functional mesoporous phenolic resin(SH-MPs-H) which has regular pore structure, abundant thiol and a large specific surface area can used for the remove of heavy metal ion. When compared with activated carbon and ordered mesoporous phenolic resin, it shows good adsorption performance. On the other hand, the thiol can be oxidized into sulfonic group to obtain the SO3H-MPs-H material. It can be used as acid catalysts for catalyzing esterification reaction and show good reactivity. In addition, SH-MPs-H can alao react with gold chloride acid to prepare bifunctional catalyst(Au-SH/SO3H-MPs-H), which shows better activity. This is due to the rich thiol of SH-MPs-H which makes the catalyst capture more gold nanoparticles. So the distance of the gold nanoparticles becomes smaller improving the catalytic activity of the catalyst.3. Using the method of hydrothermal synthesis method, we prepared thiol functional mesoporous phenolic resin spheres(SH-MPN). Compared with SH-MPs, SH-MPN has a much shorter channel and neat morphology. Its particle size is about 150 nm. These advantages can help molecule’s transfer and diffusion. Through the redox reaction between the thiol and gold chloride acid, we can also get the bifunctional catalysts Au-SH/SO3H-MPN. The catalyst has better activity than Au-SH/SO3H-MPs because of its much shorter channel and neat morphology. Furthermore, it can also catalyze silane hydrolysis reaction.