| Since the first discovery of ordered mesoporous silicas (MS41) by Mobile scientists, mesoporous materials have attracted much more attentions and have been widely used in the fields of adsorption, catalysis, separation, and host-guest chemistry and physics due to its novel properties including ordered mesostructure, high BET surface area, large pore sizes, uniform pore array, large pore volumes and various framework compositions. Especially in the last decades, ordered mesoporous materials have been widely synthesized and researched by many scientists in the world, with the increasing needing for practical applications, it was found that the stabilities especially the hydrothermally stability strongly constrain the widely applications of mesoporous materials, many people have tried various methods to improve the stability of mesoporous materials, among which the high temperature syntheses was thought to be an effective way to enhance the hydrothermal stability of mesoporous materials, however, relatively high-temperatures (>200℃) will result in the decomposition of surfactant templates, giving disordered mesostructure due to the surfactant molecules will not be able to direct mesoporous structure in such unfavorable conditions for micelle formation. The strategy for high-temperature synthesis of ordered mesoporous materials is firstly reported by Xiao et al, and they successfully synthesized a series of stable mesoporous silica with very high degree of silica condensation using the mixture of copolymer and fluorocarbon surfactant or solo hydrocarbon surfactant as the templates at about 190℃, but when the temperature was up to 200℃, it will difficult to keep the ordered mesostructure for silicas due to its rigid network. From the inspiration of high temperature syntheses of silicas, we successfully synthesized ordered mesoporous phenol-formaldehyde resin at much higher temperature (up to 260℃) using solo hydrocarbon surfactant as the templates, which was due to the industrial phenol-formaldehyde resin was usually synthesized at the temperature higher than 220℃, more interestingly, we found that the high temperature products including ordered mesoporous resin (k value as low as 2.35) or silicas (k value as low as 1.34) exhibit excellent insulated properties, giving very lower dielectric constants, the above results have not been reported previously.The replacement of mineral liquid acids by solid acids for the production of fine chemicals has been paid much attention due to the advantages of easy separation of the catalyst from the reaction medium, reductive corrosion, improved regenerability, and enhanced product selectivity. Typically solid acids are zeolites, heteropolyacids, sulfated metal oxides, and ion-exchange resins. Among these solid acid catalysts, zeolites are of great importance because of their high surface area, versatile framework, controllable acid strength and shape-selectivity. However, bulky molecules cannot get access to the catalytically active sites in relatively small micropores in zeolites, which strongly influences the catalytic conversion of bulky substrates. Synthesis of ordered materials such as MCM-41 and SBA-15 offers a totally new route to solve the limitation of micropores, but the amorphous nature of mesoporous walls hinders their catalytic applications as strong acidic catalysts for conversion of bulky molecules. To achieve strong acidic sites, sulfonic groups have been successfully incorporated into the mesoporous walls by various routes, giving excellent catalytic properties in a series of acid-catalyzed reactions. Notably, there is a strict limitation on the concentration of sulfonic groups on mesoporous materials because a large amount of sulfonic groups normally lowers the sample mesoporosity. Additionally, the presence of hydrophilic terminal silanols on the surface of mesoporous materials also influence their catalytic properties. Because the water usually act as a by-product of the reaction co-adsorbs near the acidic active centers, resulting in their partial deactivation due to competition with the alcohol reactant species. Compared with mesoporous silica walls, organic frameworks have hydrophobic features, which might result in new solid acids by modification of sulfonic groups. For example, sulfonated resins are good acidic catalysts, but their shortcomings such as low surface area and stability are still challengeable. Recently, Xing et al have successfully synthesized SO3H-functional FDU-type mesoporous phenol-formaldehyde resins (FDU-n-SO3H, n=14 and 15), which showed superior catalytic activities in the liquid-phase Beckmann rearrangement of cyclohexanone oxime and the condensation of bulky aldehydes with alcohols. These novel solid catalysts have high surface areas (up to 539 m2/g) and controllable hydrophobicity, but their acidic concentration is still blocked by the limitation to sulfonation in the phenolic rings due to the strong steric hindrance. Therefore, SO3H-functionalized porous organic materials with large surface area and high concentration of sulfonic groups as well as good stability are strongly desirable. More recently, we have synthesized mesoporous polydivinylbenzenes (PDVB-xs) with large surface area and pore volume. When compared with mesoporous phenol-formaldehyde resins, they exhibited excellent stability, good swelling property, high capacity for functionalization, and super hydrophobicity due to the unique polymerization of divinylbenzene (DVB) under hydrothermal conditions. We demonstrated here a successful synthesis of sulfonated mesoporous PDVB-xs (PDVB-x-SO3Hs) with large surface area and high content of sulfonic groups. Catalytic tests showed that these PDVB-x-SO3Hs are more catalytically active in esterification and Friedel-Crafts acylation than conventional strongly acidic ion-exchange resin (Amberlyst 15:copolymer of sulfonated polystyrene with PDVB), arenesulfonic and propyl-sulfonic groups functional mesoporous silicas (SBA-15-Ar-SO3H and SBA-15-Pr-SO3H).From the syntheses of the novel mesoporous PDVB samples, we demonstrate here a successfully syntheses of novel mesoporous solid base with polymer networks. In recent years, the production of biodiesel from renewable resources has been attracted much attention due to increasing requirement of the energy, and one of the most important ways for solving this problem is transesterifications of triglycerides with short-chain alcohols, normally catalyzed by acids and bases. Liquid acids such as H2SO4 exhibit good catalytic activity, but their environmentally unfriendly properties such as strong corrosion and difficult recyclability severely hinder their applications. Solid acids such as sulfated zirconia and supported heteropolyacids have advantages such as good catalyst recycling and high stability for poisoning CO2 in air, but the relatively low activities, coverage, and leaching of active sites on these catalysts are difficult to apply in industrial processes. Compared with acids, base catalysts are very active. Industrially, homogeneous base catalysts such as NaOH and KOH are preferred due to their wide availability and low cost, but the environmental concerns and catalyst regeneration strongly limit their applications. Solid bases have similar activities to those of homogeneous base catalysts, but their sensitive active sites poisoned by molecules such as H2O, CO2, and fatty acids (FFAs) existed in crude vegetable oils are still a great challenge. In these solid catalysts, many factors such as textural parameters, wettability, and adsorption features strongly influence their catalytic properties. Particularly, hydrophobic catalysts are very helpful to significantly enhance activities in transesterifications of triglycerides with methanol. It is notable that a series of super-hydrophobic materials with versatile compositions have been fabricated rationally, but the combination of solid catalysts with super-hydrophobic feature is still unsuccessful yet. We have demonstrated here a super-hydrophobic and porous solid base via a copolymerization of divinylbenzene and 1-vinylimidazolate (PDVB-VI). Catalytic tests in methanol transesterifications of tripalmitin as well as virgin plant oil show that PDVB-VI exhibits unprecedentedly high activities and excellent catalyst stability as well as extraordinary regeneration ability, compared with conventional bases and monomer and polymer of vinylimidazolate, which is of great importance for production of clean biodiesel from low-cost renewable feedstocks.Except for the imidazolate group functional super-hydrophobic mesoporous polymers, we also successfully introduce pyridine, and pyrrolidone groups onto the network of mesoporous polymers, further quaternary ammoniated by CH3I, r and 1.3-propanesultone, followed by exchange by HBF4, HSO3CF3, H2SO4, HPF6,H3O40PW12, resulting in the novel ionic liquids functional hydrophobic mesoporous polymers. In recent years, room temperature ionic liquids (ILs) have attracted much attention due to their green and promising solvents for synthetic chemistry and widely applications in the field of catalysis especially act as acidic catalyst. Acidic ionic liquids, including the well-known chloroaluminate based ionic liquids and the recently developed Br(?)nsted acidic ones that contains tri-fluoromethyl sulfuric acid as acidic group, have proved to be effective catalysts for a variety of reactions. Compared with homogeneous catalytic system, chemical industry prefers heterogeneous catalysts due to their advantages such as ease of separation, the possiblity of using fixed-bed reactor, enhanced recycle ability and green chemical processes; furthermore, the use of a biphasic reaction system requires a large amount of IL, and on the basis of economic criteria and possible toxicological concerns, it is desirable to minimize the amount of utilized IL in reaction processes. The immobilization of ionic liquids onto solid supports by chemical covalent bond results in new kinds of novel heterogeneous catalysts, which opened a new way to solve problems produced by conventional room temperature ionic liquids. Up to now, the most conventional supporters for immobilizing the ionic liquids were inorganic frameworks such as mesoporous silica-alumina, zeolites, which have achieved much better catalytic activities and renewable ability. Considering the silica framework is unstable against fluoride ions, water, and acids; in the meanwhile, the high content of immolization of ILs onto mesoporous silicas will also destroy the ordering of mesopores. To overcome the above problems, Kim eta successfully immobilized the ionic liquids on to polystyrene-based polymer, which opened a new way for immolizing ILs on organic frameworks, the organic supporter was ensentive to water and various acids. However, the complex synthetic processes and the low surface area of resulted heterogeneous catalyst may constrain its widely applications, the low surface area was not helpful for catalytic reactions due to catalysis was a surface phenomenon, the low surface area will constrain the tranmission of the substances. Additionally, all of above reported ILs supporters exhibit hydrophilic property, and in many acidic reactions, water ususlly act as byproduct, which would influence the reaction equilibrium, deactivation of active sites. There were many successes for synthesizing mesoporous polymers, which have large surface, different pore size distribution and adjustable hydrophilic-hydrophobic property. However, immobilizing the homogeneous acidic ILs catalysts onto mesoporous polymer is still unsuccessful yet. We demonstrated here a facile method to immobilize homogeneous acidic ILs onto super-hydrophobic mesoporous polymer for the first time. We firstly synthesized super-hydrophobic mesoporous polymer through the copolymerization of divinylbenzene with functional monomer including 1-vinylimidazolate, 4-vinylpyridine and 1-vinyl-2-pyrrolidone under solvothermal conditions, which have been published previously, named by PDVB-[mim]. PDVB-[pyr] and PDVB-[pyrr], then the as made mesoporous polymers were quaternary ammonization by CH3I, CH2CH2CH2CH2Br and 1.3-propanesultone resulting in the products of PDVB-[Cnmim], PDVB-[Cnpyr], and PDVB-[Cnpyrr], (Where Cn stands for the length of aliphatic chain), after exchanging with various acids including HBF4, HSO3CH3, H2SO4, HPF6, H304oPW12 various ionic liquids functional mesoporous polymer PDVB-[Cnmim][X], PDVB-[Cnpyr][X], PDVB-[Cnpyrr][X] (where X stands for the negative ion of the correspondingly acids) were obtained. The resulted solid acids exhibits novel characterizations such as high surface area, adjustable contents of active sites, and hydrophobic property. More interesting, this type of solid acids exhibit excellent catalytic activities in Peckmann reaction of resorcinol with ethyl acetoacetate, Kharasch addition of styrene with CCl4, and nitration reaction of toluene with HNO3 solution than commerical solid acids catalysts including Amberlyst 15, sulfonic groups functional mesoporous silicas (SAB-15-SO3H) and ILs modified SAB-15, which were even comparable with that of sulfuric acid, and correspondingly acidic homogeneous ILs.In recent years, aluminosilicate zeolites with intricate micropores and strong acidity have been widely used as heterogeneous catalysts in industrial petrochemistry and fine chemical synthesis. However, relatively small and sole micropores in zeolites strongly hinder the diffusion of reactants and products and catalytic conversion of bulky molecules. To overcome this problem, a route for synthesizing zeolite nanocrystals is shown at first, but the separation of zeolite nanocrystals from a slurry mixture is difficult. Recently, many great efforts are put to introduce mesopores/mesoporosity in zeolites through templating strategies. Notably, these mesopores are randomly distributed and controlling mesoporous orientation in zeolites still remains a challenge. Possibly, the formation of ordered mesopores in zeolites requires bending the rigid aluminosilicate zeolite units. The smaller ordered micelle should have larger curvature of zeolite units, hence leading to higher bending force. Therefore, even if ordered mesostructured carbon of CMK-3 with smaller pores (3-6 nm) is used as hard template, the mesopores in zeolite are still disordered. However, when the ordered mesostructured carbons are large enough (10-40 nm), ordered mesoporosity in aggregated zeolites could be obtained. In contrast, if there is no bending force for rigid zeolite units, stable single-unit-cell nanosheets of zeolite MFI are successfully prepared in the presence of designed bifunctional surfactants. These results suggest that relatively large templates might be favorable for the formation of mesoporous zeolites with controllable orientation. Despite of successful applications for large micelle in strongly acidic aqueous solution (e. g. triblock polymer of P123 and copolymer of PS215-PEO100) in recent years, it is still difficult to obtain the large micelle under the conditions in which zeolites are synthesized. Here we show that appropriately designed amphiphilic copolymers with high molecular weight can direct the formation of ZSM-5 zeolite crystals with b-axis-oriental mesopores (ZSM-5-OM). The opened mesopores in ZSM-5-OM are very helpful for catalytic conversion of bulky organic molecules. Normally, amphiphilic copolymers are difficult to interact with silica species in basic media. Therefore, conventional amphiphilic copolymers are not easy to template mesoporosity formed in zeolitic crystals. In our case, copolymer polystyrene-co-4-polyvinylpyridine (molecular weight about 1.6×105, PSt-co-P4VP) was treated with methyl iodide, forming a cationic copolymer (C-PSt-co-P4VP), which could be highly dispersed in silica gels because the positive charge is favorable to interact with negative charge of silica species in the synthesis of zeolites.
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