• 대한금속재료학회지
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• 제47권8호
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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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• 제12권1호
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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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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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.

• 폴리머
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• 제26권4호
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• pp.445-451
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• 2002

본 연구에서는 실리카의 표면처리를 위해 실란 커플링제인, ${\gamma}$-methacryloxy propyl trimethoxy silane (MPS), ${\gamma}$-glycidoxy propyl trimethoxy silane (GPS), and ${\gamma}$-mercapto propyl trimethoxy silane (MCPS) 등을 사용하여 실리카 흡착특성과 기계적 계면물성에 대하여 고착하였다. 실란처리에 따른 실리카의 평형 확산압력, 표면 자유에너지, 비표면적을 BET법을 이용한 $N_2$/77 K 기체 흡착을 통하여 알아보았다. 본 실험결과 신란처리에 의해 실리카 표면에 도입된 비극성 관능기로 인해 실리카의 비표면적, 평형 확산압력, 표면 자유에너지의 비극성 요소가 증가하였으며 결과적으로 실리카/고무 복합재료의 기계적 계면 물성인 tearing energy ($G_{mc}$)가 향상되었음을 확인할 수 있었다. 그리고 MPS로 표면처리한 경우가 GPS, MCPS에 비해서 우수한 기계적 계면물성을 나타남을 관찰할 수 있었다.

• 한국결정성장학회지
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• 제22권6호
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• pp.291-298
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• 2012

자기 조립 분자 집합체 물질인 CMPO로 표면개질 된 메조 다공성 실리케이트를 가수분해와 축합반응을 이용하여 합성하였다. 손님 물질인 CMPO는 2-(diphenylphosphoryl) acetic acid와 3-(triethoxysilyl) propan-1-amine의 아마이드 결합반응을 이용하여 합성하였으며, MCM-41, SBA-15 그리고 실리카 나노입자와 같은 다양한 메조 다공성 실리케이트는 주인물질로 채택하였다. 메조 다공성 실리케이트의 비표면적은 680 $m^2/g$~1310 $m^2/g$의 넓이로 측정되었으며 BJH 방법을 이용해서 동공의 크기를 확인한 결과 2.3~9.1 nm 범위의 다양한 크기를 가지고 있었다. 메조 다공성 실리카 중에서는 SBA-15(II)가 가장 높은 약 35 wt%의 CMPO 함유량을 나타내었다. 메조 다공성 실리케이트의 표면에 개질된 CMPO 실란 작용기와 란탄족 이온과의 접근성에 관한 연구 결과, CMPO로 개질 된 모든 흡착제의 경우 상대적으로 이온 반경이 큰 La(III)보다는 크기가 작은 Nd(III)와 Eu(III) 이온을 더 선호하였다.

• Elastomers and Composites
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• 제40권1호
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• pp.22-28
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• 2005

본 연구에서는 실리카/고무 복합재료의 기계적 계면 물성과 열안정성에 대한 산소플라즈마의 영향에 대하여 살펴보았다. 실리카의 표면특성은 XPS와 접촉각 측정을 통하여 살펴보았다. 실리카/고무 복합재료의 기계적 물성과 열안정성은 각각 인열에너지 ($G_{IIIC}$)와 열중량분석(TGA)를 통하여 관찰하였다. 실험결과, 플라즈마 처리시간이 증가함에 따라 실리카 표면에 산소가 함유된 극성 관능기의 도입량이 증가하였으며, 이에 따라 고무 복합재료의 인열에너지와 열안정성이 향상되었다. 이러한 결과는 NBR과 같은 극성고무가 산소가 함유된 관능기가 도입된 실리카와 상대적으로 높은 상호작용을 하기 때문으로 판단된다.

• 폴리머
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• 제39권1호
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• pp.169-173
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• 2015

3-Aminopropyltrimethoxysilane(1NS) 또는 N-[3-(trimethoxysilyl)propyl]ethylenediamine(2NS)으로 표면 기능화된 실리카에 1-butyl-4-methylpyridinium chloride(Cl)와 tributylmethylammonium chloride(Amm), benzyldimethyltetradecylammonium chloride(Ben), 1-butyl-1-methylpyrrolidinium chloride(Pyr)와 같은 이온성 액체를 이용하여 표면처리한 후 메탈로센 촉매를 담지하여 에틸렌 중합을 실시하였다. $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ 촉매와 $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ 촉매의 Zr 함량은 아미노실란 화합물로만 표면 처리된 촉매보다 감소하였다. $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ 촉매의 중합 활성은 $SiO_2/1NS/(n-BuCp)_2ZrCl_2$ 촉매보다 증가하였다. 반면, $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$은 Zr 함량의 감소로 중합 활성은 $SiO_2/2NS/(n-BuCp)_2ZrCl_2$ 촉매에 비해 감소하였다.

• 대한치과보철학회지
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• 제41권5호
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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.

• 공업화학
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• 제27권1호
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• pp.86-91
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• 2016

Ionic liquid 기능화 및 메탈로센 촉매 담지를 위해 세 종류의 무정형 실리카와 SBA-15를 담체로 사용하였다. Ionic liquid가 표면 기능화된 실리카는 1,3-bis(cyanomethyl)imidazolium chloride의 염소 음이온과 실리카 표면의 OH 그룹 사이의 상호작용에 의해 합성되었다. 에틸렌 중합을 위해 ionic liquid가 기능화된 실리카에 메탈로센과 조촉매 methylaluminoxane(MAO)을 담지하였다. SBA-15와 비교하여 큰 기공 크기를 갖는 ionic liquid가 표면 기능화된 XPO-2412와 XPO-2410에 담지된 촉매는 기능화되지 않은 실리카에 담지된 촉매보다 높은 활성을 보였다. 그러나 SBA-15에 담지된 촉매는 ionic liquid의 표면 기능화 후에 활성이 감소하였다. 이는 ionic liquid와 메탈로센 촉매, 조촉매 MAO가 담지되면 기공의 크기가 크게 줄어들기 때문에 중합 시 에틸렌 모노머와 조촉매가 기공 내 촉매 활성점으로 확산하는데 제한을 받기 때문이다. 또한 실리카 표면의 OH 그룹의 농도 변화에 따른 촉매의 중합 활성에 대한 영향을 연구하였다. 무정형 실리카의 OH 그룹의 농도가 증가할수록 중합 활성도 증가하였으며 실리카에 담지된 촉매의 중합 활성은 ionic liquid 표면처리 후에도 유사한 경향을 보였다.

• 통합자연과학논문집
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• 제2권1호
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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.