• Korean Journal of Metals and Materials
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• v.47 no.8
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• pp.516-521
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• 2009

In this study we report a rapid synthesis of nanoporous organo-functional silica (OFS) with unimodal and bimodal pore structures encompassing pores ranging from meso-to macroscale. The problems of tediousness and high production cost in the conventional syntheses are overcome by co-condensation of an inexpensive inorganic precursor, sodium silicate with an organosilane containing trimethyl groups. The insitu covalent anchoring of the non-polar trimethyl groups to the inner pore walls prohibits irreversible shrinkage of the wet-gel during microwave drying at ambient pressure and thus larger size pores (from ca. 20 to ca. 100 nm) can be retained in the dried silica. The drying process of the silylated wet-gels at an ambient pressure can be greatly accelerated upon microwave exposure instead of drying in an oven or furnace. Using this approach, anoporous and superhydrophobic silicas showing a wide variation in texture and morphology can be readily synthesized in roughly two hours. The effects of various sol-gel parameters solely on the textural properties of the organo-functional silica (OFS) have been investigated and discussed.

• Advances in nano research
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• v.12 no.1
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• pp.49-63
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• 2022

Nanocatalysts are usually used in the synthesis of petrochemical products, fine chemicals, biofuel production, and automotive exhaust catalysis. Due to high activity and stability, recyclability, and cost-effectiveness, nanocatalysts are a key area in green chemistry. On the other hand, water as a common by-product or undesired element in a range of nanocatalyzed processes may be promoting the deactivation of catalytic systems. The advancement in the field of hydrophobicity in nanocatalysis could relatively solves these problems and improves the efficiency and recyclability of nanocatalysts. Some recent developments in the synthesis of novel nanocatalysts with tunable hydrophilic-hydrophobic character have been reviewed in this article and followed by highlighting their use in catalyzing several processes such as glycerolysis, Fenton, oxidation, reduction, ketalization, and hydrodesulfurization. Zeolites, carbon materials, modified silicas, surfactant-ligands, and polymers are the basic components in the controlling hydrophobicity of new nanocatalysts. Various characterization methods such as N2 adsorption-desorption, scanning and transmission electron microscopy, and contact angle measurement are critical in the understanding of hydrophobicity of materials. Also, in this review, it has been shown that how the hydrophobicity of nanocatalyst is affected by its structure, textural properties, and surface acidity, and discuss the important factors in designing catalysts with high efficiency and recyclability. It is useful for chemists and chemical engineers who are concerned with designing novel types of nanocatalysts with high activity and recyclability for environmentally friendly applications.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.199-199
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• 2011

The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

• Polymer(Korea)
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• v.26 no.4
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• pp.445-451
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• 2002

In this work, the adsorption characteristics and mechanical interfacial properties of treated silicas by silane coupling agents, such as, ${\gamma}$-methacryloxy propyl trimethoxy silane (MPS), ${\gamma}$-glycidoxy propyl trimethoxy silane (GPS), and ${\gamma}$-mercapto propyl trimethoxy silane (MCPS), were investigated. The equilibrium spreading pressure ($pi_e$), surface free energy ($gamma_s$ s/), and specific surface area ($S_{BET}$) were studied by the BET method with $N_2$/77 K adsorption. The developments of nonpolar functional groups of the silica surfaces treated by silane coupling agents led to the increase in the $S_{BET}$, $pi_e$, and $gamma_s$, resulting in the improved tearing energy ($G_{mc}$)of the silica/rubber composites. The composites treated by MPS showed the superior mechanical interfacial properties in these systems. These results explained by changing of crystalline size, dispersion, agglomerate, and surface functional group of silica/rubber composites.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.22 no.6
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• pp.291-298
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• 2012

Carbamoylphosphate (CMPO) [CMPO analogue; 2-(diphenylphosphoryl)-N-(3-(triethoxysilyl)propyl)acetamide]silane, as a functional self-assembled molecules, grafted mesoporous silicates were prepared by simple hydrolysis and condensation reaction. Pore sized tailored mesoporous silicates such as MCM-41, SBA-15, or amorphous silica nanoparticles were adopted as host materials. The surface area of ordered mesoporous silicates was ranged from 680 $m^2/g$ to 1310 $m^2/g$ with different pore diameters that estimated to be ca. 2.3~9.1 nm by BJH method. Among the OMMs host materials, SBA-15(II) has higher loading ratio (~35 wt%) of CMPO derivative than other OMMs. Accessibility to CMPO silane functional groups in the surface of mesoporous silicas was studied by lanthanide ions sorption experiments. All of the CMPO modified OMMs favors the smaller Eu(III) and Nd(III) cations than La(III) for relative larger ionic radius.

• Elastomers and Composites
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• v.40 no.1
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• pp.22-28
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• 2005

In this work, the effect of oxygen plasma treatment of nano-scaled silica on the mechanical interfacial properties and thermal stabilities of the silica/rubber composites was investigated. The surface properties of the silica were studied in X-ray photoelectron spectroscopy (XPS) and contact angles. And, their mechanical interfacial properties and thermal stabilities of the composites were characterized by tearing energy ($G_{IIIC}$) and thermogravimetric analysis (TGA), respectively. As a result, it was found that the introduction rate of oxygen-containing polar functional groups onto the silica surfaces was increased by increasing the plasma treatment time, resulting in improving the tearing energy. Also, the thermal stabilities of the composites were increased by increasing the treatment time. These results could be explained that the polar rubber, such as acrylonitrile butadiene rubber (NBR), showed relatively a high degree of interaction with oxygen-containing functional groups of the silica surfaces in a compounding system.

• Polymer(Korea)
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• v.39 no.1
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• pp.169-173
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• 2015

Metallocene was supported on the silica, which was functionalized with aminosilanes such as aminopropyltrimethoxysilane (1NS) or N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), and ionic liquids such as 1-butyl-4-methylpyridinium chloride (Cl), tributylmethylammonium chloride (Amm), benzyldimethyltetradecylammonium chloride (Ben), 1-butyl-1-methylpyrrolidinium chloride (Pyr), and then ethylene polymerizations were performed. The Zr contents of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ and $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ were lower than those of only aminosilane-treated silicas. However, the polymerization activity of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ was higher than that of $SiO_2/1NS/(n-BuCp)_2ZrCl_2$. The polymerization activity of $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ was lower than that of $SiO_2/2NS/(n-BuCp)_2ZrCl_2$ due to much lower Zr content.

• The Journal of Korean Academy of Prosthodontics
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• v.41 no.5
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• pp.606-616
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• 2003

Purpose : The purpose of this study was to research the properties of some chemically cured methacrylate polymers such as MMA, HEMA, TEG-DMA, bis-GMA, GMA. Material and Method : 5 kinds of methacrylates were selected and added 2% tertiary amine and benzoyl peroxide to make a chemically curable polymer 25 micron crushed silicas which are treated with silane were selected as filler, they were added into methacrylate monomer until the consistency did not changed by the load of 500gram. All of the experimental resins were 5 kinds, and a serial test was done with 3 kinds of items including the filler contents, the tensile strength, and the bond strength. The number of specimen were 10 for each group. Filler contents were obtained by reducing the specimens to ashes at $600^{\circ}C$ for 1 hour. The specimens with the dimension of 6mm in diameter and 3mm thick were immersed in $37{\pm}1^{\circ}C$ distilled water for 24 hours before test, and tensile strength were measured with cross-head speed 1mm/min. Shear bond strength were mea sured on the specimens attached to bovine enamel etched with 37% phosphoric acid for 1 minute. Results : 1. Maximum filler incorporation was the highest as 75.5% on MMA, and the least as 53.4% on bis- GMA(p<0.0001). 2. The tensile stregth were MMA 141.3, GMA 154.3, TEG-DMA 157.4, bis-GMA 161.4 MPa, and HEMA showed the highest value, 226.9MPa(p = 0.0004). 3. The bond strength were GMA 10.1, TEG-DMA 11.7, HEMA 12.2, bis-GMA 13.3 MPa, and MMA showed the highest value, 15.3MPa, however statistical significances were not (p =0.3838), 4. TEG-DMA and HEMA were not different on the aspect of maximum filler contents and shear bond strength(p>0.05). Conclusion : HEMA can be used as an another diluent substituting TEG-DMA with the increased strength and with the constant bond strength and the constant filler contents.

• Applied Chemistry for Engineering
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• v.27 no.1
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• pp.86-91
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• 2016

Three amorphous silicas and SBA-15 were employed as supports, which were capable of confining ionic liquid (IL) and metallocene in the nanopore. Ionic liquid functionalized silica was prepared by the interaction between the chloride anions of 1,3-bis(cyanomethyl)imidazolium chloride and the surface OH groups. Metallocene and methylaluminoxane (MAO) were subsequently immobilized on the ionic liquid functionalized silica for ethylene polymerization. The metallocene supported on ionic liquid functionalized XPO-2412 and XPO-2410 having a larger pore diameter compared to SBA-15 showed higher activity than that of using supported catalyst without ionic liquid functionalization. However, the activity of metallocene supported on SBA-15 decreased after ionic liquid functionalization, suggesting that the diffusion of ethylene monomer and cocatalyst to the active site of nanopore was restricted during ethylene polymerization. This could be resulted from significant reduction of the pore diameter due to the immobilization of ionic liquid and $(n-BuCp)_2ZrCl_2$ and MAO. The effect on polymerization activity in accordance with the concentration of hydroxyl groups on the surface was also investigated. The polymerization activity increased as the concentration of hydroxyl groups on amorphous silica increased. The polymerization activities of metallocene supported on silica showed the similar trend after ionic liquid functionalization.

• Journal of Integrative Natural Science
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• v.2 no.1
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• pp.18-23
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• 2009

This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.