• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.274-279
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• 1992

Immobilization method of lariat azacrown ethers, containing hydroxyl group in the side arm of crown ring, on the polymer matrix and the phase-transfer catalytic activity of thus obtained immobilized lariat azacrown ethers were studied. Polystyrene resins with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of crosslinked polystyrene resins containing epoxy groups with monoaza-15-crown-5 or monoaza-18-crown-6. Microporous crosslinked polystyrene resins containing epoxy group for the syntheses of these immobilized lariat crown catalysts were prepared by suspension polymerization of styrene, divinylbenzene (DVB 2%) and vinylbenzylglycidyl ether. The immobilized lariat catalysts with 10-20% ring substitution exhibited maximal activity for the halogen exchange reactions of 1-bromooctane with aqueous KI or NaI under triphase heterogeneous conditions. Immobilized catalyst exhibited higher activity than corresponding catalyst without the hydroxyl group and this result was suggested that the active site have a structure in which the $K^+$ ion was bound by the cooperative coordination of the crown ring donors and the hydroxyl group in the side arm.

• Carbon letters
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• v.11 no.1
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• pp.38-40
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• 2010

Carbon supported electrocatalysts are commonly used as electrode materials for polymer electrolyte membrane fuel cells(PEMFCs). These kinds of electrocatalysts provide large surface area and sufficient electrical conductivity. The support of typical PEM fuel cell catalysts has been a traditional conductive type of carbon black. However, even though the carbon particles conduct electrons, there is still significant portion of Pt that is isolated from the external circuit and the PEM, resulting in a low Pt utilization. Herein, new types of carbon materials to effectively utilize the Pt catalyst are being evaluated. Carbon nanofiber/activated carbon fiber (CNF/ACF) composite with multifunctional surfaces were prepared through catalytic growth of CNFs on ACFs. Nickel nitrate was used as a precursor of the catalyst to synthesize carbon nanofibers(CNFs). CNFs were synthesized by pyrolysising $CH_4$ using catalysts dispersed in acetone and ACF(activated carbon fiber). The as-prepared samples were characterized with transmission electron microscopy(TEM), scanning electron microscopy(SEM). In TEM image, carbon nanofibers were synthesized on the ACF to form a three-dimensional network. Pt/CNF/ACF was employed as a catalyst for PEMFC. As the ratio of prepared catalyst to commercial catalyst was changed from 0 to 50%, the performance of the mixture of 30 wt% of Pt/CNF/ACF and 70wt% of Pt/C commercial catalyst showed better perfromance than that of 100% commercial catalyst. The unique structure of CNF can supply the significant site for the stabilization of Pt particles. CNF/ACF is expected to be promising support to improve the performance in PEMFC.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.593-602
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• 1988

Polymer-supported crown ethers (Ps-CE) which can be used for phase-transfer catalyst (PTC) were synthesized for the purpose of allowing reusable function to ordinary crown ethers, and the kinetics of the liquid-solid-liquid triphase-catalyzed nucleophilic displacement reaction of iodide (aqueous phase) on 1-bromooctane (organic phase) using synthesized Ps-CE (solid) were studied. Ps-CE were obtained by grafting of hydroxymethyl crown ethers to 1~2% cross-linked chloromethylated polystyrene. All reactions followed a pseudo-first order dependency on the 1-bromooctane concentration and the observed rate constants $(k_{obsd})$ were linearly related to the molar equivalents of Ps-CE, and were subjected to the influence of cross-linking density of polymer backbone, solvent and the reaction temperature. The catalytic activity of Ps-CE was also compared with that of structurally similar soluble crown ethers, and used Ps-CE were easily recovered after the reaction by simple filtration and could be reused without loss of catalytic activity in the same anionic displacement reaction. Enthalpies and entropies of activation associated with the displacement were 10~20kcal $mol^{-1}, 20~55eu. respectively, and the free energy of activation was ~30kcal mol^{-1}$.

• Particle and aerosol research
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• v.11 no.3
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• pp.87-92
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• 2015

MCM-41 (Mobil Composition of Matter) and SBA-15 (Santa Barbara Amorphous) were used as a supported catalyst for ethylene polymerization due to their combination of large surface area and wide range of pore size distribution. The morphology of supports was used to control the morphology of the resulting polymer. Different molar ratios of Al/Ti were used for ethylene polymerization at $60^{\circ}C$ under atmospheric pressure. The effect of different mass ratios of MCM-41/SBA-15 and 1-hexene concentration on polymerization activity and polymer properties was investigated. The catalytic activity and the crystallinity reached the highest value at Al/Ti of 480. Upon incorporation of MCM-41 and SBA-15 into $MgCl_2/TiCl_4$ catalyst, the molecular weight and crystallinity of polyethylene were enhanced. The obtained polyethylene showed melting temperature between 130 and $135^{\circ}C$. The polyethylene with replication structure of support and bimodal MWD was expected.

• Applied Chemistry for Engineering
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• v.29 no.1
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• pp.62-66
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• 2018

Styrenated phenol alkoxylates (SP-A) were prepared from styrenated phenol (SP) and ethylene oxide (EO) under a homogeneous base catalyst. However, to use EO that is difficult to handle, a high-pressure reaction device capable of controlling the reaction process should be used. Additionally, when a homogeneous base catalyst is used, a neutralization process is required to remove residual bases after the reaction, and it is also difficult to separate the catalyst and the product. Therefore, in this study, we report the results of SP-A prepared from the reaction of SP and EC using only heterogeneous base catalysts. The heterogeneous base catalyst was obtained by supporting KOH on $La_2O_3$ and calcintion. Using EC instead of EO, it was possible to produce SP-A under the atmospheric rather than high-pressure reaction condition. Average molecular weights of synthesized SP-A varied greatly depending on reaction conditions. The average molecular weight of SP-A prepared using the $KOH/La_2O_3$ catalyst could be controlled arbitrarily by controlling the reaction temperature and added catalyst and EC amounts.

• Journal of the Korean Society for Precision Engineering
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• v.31 no.10
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• pp.955-965
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• 2014

Transport phenomena of reactant and product are directly linked to intrinsic inhomogeneous random configurations of catalyst layer (CL) that consist of ionomer, carbon-supported catalyst (Pt/C), and pores. Hence, electrochemically active surface area (ECSA) of Pt/C is dominated by geometrical morphology of mass transport path. Undoubtedly these ECSAs are key factor of total fuel cell efficiency. In this study, non-deterministic micro-scale CLs were randomly generated by Monte Carlo method and implemented with the percolation process. To ensure valid inference about Pt/C catalyst utilization, 600 samples were chosen as the number of necessary samples with 95% confidence level. Statistic results of 600 samples generated under particular condition (20vol% Pt/C, 30vol% ionomer, 50vol% pore, and 20nm particle diameter) reveal only 18.2%~81.0% of Pt/C can construct ECSAs with mean value of 53.8%. This study indicates that the catalyst utilization in fuel cell CLs cannot be identical notwithstanding the same design condition.

• Korean Journal of Metals and Materials
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• v.47 no.7
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• pp.454-459
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• 2009

In order to commercialize Polymer Electrolyte Fuel Cell (PEFC), the cathode catalyst such as Platinum supported Carbon (Pt/C) need to have a high activity of Oxygen Reduction Reaction (ORR). In this study, the 20% Pt/C was synthesized using the chemical reduction method while the crystallinity of Platinum (Pt) particles were controlled under heat treatment conditions. The activity of synthesized Pt catalysts was evaluated using electrochemical measurement. Compared with the $i_{ORR}$ at 0.8 V of 20% Pt/C heat-treated at $500^{\circ}C$ and the 20% Pt/C that were not heated and commercial 20% Pt/C, the $i_{ORR}$ at 0.8 V of 20% Pt/C heattreated at $500^{\circ}C$ was 9.5 and 1.7 times higher than those of the 20% Pt/C and commercial 20% Pt/C that were not heated. It was considered that the crystallinity and particle size affect the ORR activity of the Pt/C catalysts.

• Elastomers and Composites
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• v.53 no.3
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• pp.158-167
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• 2018

In this study, in-situ trans-selective polymerization of isoprene was carried out using titanium-based Ziegler-Natta catalysts. The catalysts were prepared by high-energy ball milling. Individually Large-inner-diameter carbon nanotubes (CNTL), and hydroxylated carbon nanotubes (CNTOH), along with magnesium chloride ($MgCl_2$) were used as the carriers for the catalysts. The optimum ball-milling time for preparing the $CNT/MgCl_2/TiCl_4$ Ziegler-Natta catalysts was 4 h. The $CNTOH/MgCl_2/TiCl_4$ catalyst showed a higher efficiency than that of the $CNTL/MgCl_2/TiCl_4$ catalyst, based on the rate of polymerization. The effects of the CNT-filler type on the isoprene polymerization behaviors and polymer properties were investigated. The morphologies of the trans-1,4-polyisoprene (TPI)/CNT and TPI/CNTOH nanocomposites exhibited a tube-like shape, and the CNTL and CNTOH fillers were well dispersed in the TPI matrix. In addition, the thermal stability of TPI significantly increased upon the introduction of a small amount of both CNTL/CNTOH fillers (0.15 wt%), owing to the satisfactory dispersion of the CNTL/CNTOH in the TPI matrix.

• Polymer(Korea)
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• v.36 no.1
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• pp.111-116
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• 2012

A functionalization of mesoporous materials with organosilane was carried out via a post-synthesis grafting method and $(n-BuCp)_2ZrCl_2$/methylaluminoxane (MAO) as subsequently immobilized on the functionalized mesoporous materials for ethylene polymerization. Organosilanes having amine, cyano or imidazoline group such as $N$-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS), 4-(triethoxysilyl)butyronitrile (1NCy), 1-(3-triethoxysilylpropyl)-2-imidazoline (2NIm) were used for the surface functionalization of mesoporous materials. In the SBA-15/2NS/$(n-BuCp)_2ZrCl_2$ catalyst preparation, the amount of MAO in feed increased with an decrease in the Zr content of the supported catalyst, and Al content in the supported catalyst increased. The ethylene homopolymerization activity of SBA-15/2NS/$(n-BuCp)_2ZrCl_2$ dramatically increased as the amount of MAO in feed increased. Furthermore, when the immobilization time was 6 hrs, SBA-15/2NS/$(n-BuCp)_2ZrCl_2$ showed the highest activity. The activities of supported 2NS-, 1NCy-, 2NIm-functionalized catalysts decreased in the following order, SBA-15/2NS/ > SBA-15/2NIm/ > SBA-15/1NCy/$(n-BuCp)_2ZrCl_2$. 2NS and 2NIm which have two amine groups per silane molecule were shown to interact with $(n-BuCp)_2ZrCl_2$ strongly compared to 1NCy which has one amine group. Thus, the activities increased with an increase in the nitrogen and the Zr content of the supported catalysts.

• Applied Chemistry for Engineering
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• v.24 no.1
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• pp.55-61
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• 2013

Heterogeneous metallocene catalysts supported on montmorillonite (MMT), [$Cp_2ZrCl_2$/MMT, $Cp_2ZrCl_2$/MAO/MMT, and $Cp_2ZrCl_2$ + MAO/MMT], were prepared with three different methods of immobilization and tested for ethylene polymerization. The heterogeneous catalysts immobilized on organo clay (30B-MMT) showed the higher metal loading and polymerization activity than those immobilized on natural clay $Na^+-MMT$. These results suggest that the hydroxyl groups of organo clay interlayers react with the MAO and catalyst through the chemical bond. The metallocene catalyst supported directly on MMT showed lower activity for ethylene polymerization compared to the homogeneous systems, while MMT/MAO/$Cp_2ZrCl_2$, catalysts treated with MAO before impregnation, showed a higher activity. The polymers obtained from MMT-supported catalysts have higher melting point, molecular weight and molecular weight distributions than those of homogeneous catalysts. The polymer particles with increasing significant size. Ethylene polymerization over 30B-MMT/MAO/$Cp_2ZrCl_2$ catalyst was also performed varying the process variables to optimize the process conditions.