• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.295-301
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• 1994

The Ru(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), and Pd(Ⅱ) complexes of N$_4$-polydentate ligands(meso-Me$_6$-[14]-ane, rac-Me$_6$-[14]-ane, and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H$_2$O$_2$, t-BuOOH, and PhIO studied. The oxidations of cyclohexene, 1-hexene, cyclooctene, 1-octene, and styrene as substrates have been investigated gas chromatographically. The Ru(Ⅲ)-N$_4$ complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(Ⅲ)-N$_4$ complexes were discussed in terms of the flexibility of N$_4$-polydentate ligands, the Ru(Ⅲ)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhIO as oxidant was carried out to verify. The Pd(Ⅱ) complex turned out to be more active catalyst than the Ni(Ⅱ) complexes.

• Elastomers and Composites
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• v.48 no.1
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• pp.10-17
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• 2013

Polyolefin-g-poly(t-butylstyrene) as one of the high-temperature polyolefin-based thermoplastic elastomers was synthesized by the graft-from anionic living polymerization from the styrene moieties of the linear poly(ethylene-ter-1-hexene-ter-divinylbenzene) as a soft block to form the hard end blocks, poly(t-butylstyrene). The chemistry of the anionic graft-from polymerization involved complete lithiation of the pendant styrene unit of the soft polyolefin elastomer with sec-BuLi/TMEDA followed by the subsequent graft anionic polymerization of 4-tert-butylstyrene with Mn=10,000~30,000 g/mol. The graft-from living anionic polymerization were very effective and the grafting size increased proportionally with increasing monomer concentration and the reaction times. The synthetic methodology for the multi-hydroxyl chain-end modified polyolefin-g-poly(t-butylstyrene) was proposed by using the thiol-ene click reaction between 2-mercaptoethanol and the polyolefin-g-[poly(t-butylstyrene)-b-high vinyl polyisoprene], which was obtained from the subsequent living block copolymerization using polyolefin-g-Poly(t-butylstyrene) with isoprene. The result indicated that this process produced a new well-defined functionalized graft-type polyolefin-based TPE with high $T_g$ hard block(> $145^{\circ}C$).

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.634-638
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• 2004

Titanium silicalite-1 (TS-1) molecular sieve was produced by microwave heating of amorphous titanium-containing solid precursors after impregnation with aqueous TPAOH solution. $SiO_2-TiO_2$ xerogel, sub-micron sized $SiO_2-TiO_2$ prepared by thermal plasma process, and Ti-containing mesoporous silica, Ti-HMS, were tested as the solid phase substrates. Highly crystalline product was obtained within 30 min. after microwave irradiation with yields over 90% using $SiO_2-TiO_2$ xerogel, which showed essentially identical physicochemical properties to TS-1 prepared by conventional hydrothermal method. Excellent catalytic activity was also obtained for 1-hexene epoxidation using $H_2O_2.\;SiO_2-TiO_2$ particles prepared by thermal plasma and Ti-HMS were found inferior as a substrate for TS-1, probably due to difficulties in wetting the surface uniformly with TPAOH.

• Analytical Science and Technology
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• v.27 no.2
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• pp.100-107
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• 2014

Plastic has been widely used in modern artworks' materials due to its merits of process ability and mass production. In the country, value of plastic artifact is increasing but the field of plastic study is limited to industrial purpose. In this study, Identification methods of plastic were performed by SPME-GC/MS and pyrolysis-GC/MS using trace of samples. As a result of identification using SPME-GC/MS, aromatic compounds were identified from polyvinyl chloride. And alkane compounds were identified from polyethylene, and polypropylene. Aromatic compounds were identified from polystyrene, and diethylene glycol appeared in polyurethane based on polyester was identified from polyurethane. As a result of identification using pyrolysis- GC/MS, aliphatic alkenes compounds and phthalate(DEHP) were identified from polyvinyl chloride. Aliphatic alkenes compounds and phthalate(DIBP) were detected from polyethylene. 1-hexene, etc., were detected from polypropylene, aromatic compounds were identified from polystyrene, and methylene diphenyl diisocyanate which is polyurethane basic material was confirmed from polyurethane. This study suggested that non-destructive SPME and pyrolysis-GC/MS are useful to identify compounds particularly polystyrene and polyurethane. These two analytical methods were expected to be applied for identification of unidentified plastic artworks before conservation treatment.

• Journal of the Korean Chemical Society
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• v.62 no.3
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• Journal of Korean Society for Atmospheric Environment
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• v.20 no.6
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• pp.759-771
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• 2004

This study analyzed concentrations of volatile organic compounds (VOCs) produced from incineration of plastic wastes at $600^{\circ}C$. The plastic wastes used in this study included polyethyleneterephthlate (PETE), high density polyethylene (HOPE), polyvinyl chloride (PVC), low density polyethylene (LOPE), polypropylene (PP), polystyrene (PS) and other. Plastic wastes were heated from room temperature upto $600^{\circ}C$ providing the compressed air inside of a small-scale electric furnace for 90 minutes and then they were oxidized (incinerated) for 60 minutes at $600^{\circ}C$ maintaining the same air supply. VOCs emitted from the incineration process were sampled using an air sampling pump and Tedlar air bags for 150 minutes and then the components and concentrations of the VOCs were analyzed by a GC-MS. The most prominent chemical structure of the VOCs obtained from the incineration process of the HOPE, LOPE and PP, which include ethylene groups in their main chains, was identified as aliphatic hydrocarbons such as 1-hexene. However, aromatics such as benzene were major chemical structure from the incineration of PETE, PVC and PS which include benzene rings in their main chains. This study estimated the total VOC production from the incineration of the plastic wastes based on the real plastic waste production and the emission factors. 64% and 27% of the total VOC emissions consisted of aliphatic hydrocarbons and aromatics, respectively, which have double bonds within their molecular structure and thus a high ground level ozone formation potential.

• 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.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2737-2742
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• 2011

Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

• Polymer(Korea)
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• v.39 no.2
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• pp.346-352
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• 2015

Polyalphaolefin (PAO) is a synthetic lubricant that is superior to mineral-based lubricants in the terms of physical and chemical characteristics such as low pour point, high viscosity index (VI), and thermal and oxidation stability. Several kinds of PAOs have been synthesized by using 1-pentene, 1-hexene, 1-octene, or 1-dodecene as monomer with three kinds of aluminum-based Lewis acid catalysts via cationic polymerization. The control of the catalytic performance and physical properties of PAO such like molecular weight, kinematic viscosity, pour point, and viscosity index was done by changing polymerization parameters. The alkyl aluminum halide-based catalysts show better catalytic activity than that of the conventional $AlCl_3$ catalyst. The microstructure of PAO was investigated by means of TOF-MS (time of flightmass spectroscopy) analysis in order to elucidate the correlation between the performances of the lubricant (VI, pour point) and the molecular structure of PAO. The VI of PAO increases with increases in the carbon number of ${\alpha}$-olefin. In other words, the performances of PAO as a lubricant strongly depended on the branch length of PAO.

• Journal of the Korean Chemical Society
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• v.48 no.2
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• pp.156-160
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• 2004

The extraction rates of plasticizer of LPG high pressure rubber are studied. Submerging solvents are composed of propane, n-butane, n-pentane, n-hexane, n-heptane, propylene, 1,3-butadiene, 1-pentene, 1-hexene, ethanethiol, t-butanethiol, dimethyl sulfide, methyl ethyl sulfide. The relationship between the extraction rate of plasticizer and the descriptors of submerging solvent by using multiple linear regression is as follows; PE(wt%) = 7.5193 - 0.58500Carbon${\sharp}$ + 2.3294DB + 2364SH, (N = 13, F = 24.135, R$^2$ = 0.8894, R$_{adj}^2$ = 0.8526, Variance = 7.588) Plasticizer is well extracted by LPG composed of the high vapour pressure and polarity compounds. The mass of extracted plasticizer becomes increasing in proportion to the contents of thiol sulfur compound and unsaturated hydrocarbon such as propylene and 1,3-butadiene in LPG. While the heavier hydrocarbons are, the less the quantities of plasticizer extracted from rubber are.