• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.19 no.2
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• pp.139-152
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• 2009

According to the third study on the distribution of chemical substances carried out by the Department of Environment in 2006, there were a total of 900 chemical substances whose respective annual usage amount exceeded 1,000 tons and, among them, 90 substances belonged to the 168 hazardous substances requiring management(53.6%). The work-related illnesses caused by hazardous substances requiring management in Korea between $1992{\sim}2005$ can be classified into four groups depending on the type of the chemical substances. These four groups are 23 organic substances including benzene, 12 metals including lead, 3 acids and bases including hydrogen chloride, and 6 gaseous substances including carbon monoxide. These hazardous substances requiring management were again classified depending on the threshold limit values. The chemicals whose TLV was lower than or equal to 0.005 ppm included 4 organic substances including methylene bisphenyl isocyanate and toluene-2,4-diisocyanate (TDI). The chemicals whose TLV was larger than 51 ppm included 22 organic substances including diethyl ether and 1,2-dichloroethylene. When we classified these hazardous substances requiring management according to the categories of GHS health hazards, we found that isobutyl acetate and magnesium oxide didn't belong to the 13 health hazard categories. Among the substances whose TLV is set and whose annual usage amount is more than 0.1 million ton, we recommended 12 chemical species including 4,4'-Methylenedianiline as new hazardous substances requiring management. All the recommended substances were found to be hazardous when we classified their health hazards.

• International Journal of Safety
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• v.4 no.1
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• pp.14-17
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• 2005

Recycled polyol was obtained by glycolysis of MDI-based Polyurethane(PU) rigid foam. The chemical structure of the recycled pclyol was confirmed by GC(gas chromatography) and 1H-NMR. The recycled polyol throughout the glycolysis contained liquid polyol and methylenedianiline(MDA). MDA which could cause liver cancer is carcinogenic material. TWA(Time Weighted Average.) amount for MDA in MSDS(Material Safety Data Sheets) was confined less than 0.1 ppm. The melting temperature of MDA is $92^{\circ}C$, and boiling temperature is $398^{\circ}C$. During the gylcolysis most of MDA was dissolved in liquid polyol. The probability that MDA diffuses into the atmosphere is low but there could be an absorption of MDA into skin. Furthermore because MDA is amine compound, recycled polyol which contained MDA had a difficulty in reaction control of polyurethane. Therefore reduction of MDA amount was needed strongly. In this study the elimination of MDA were performed through deamination of the recycled polyol by glycidyl ether compounds. As glycolysis was proceeded, the amount of MDA was 9.8 wt % at early stage and increased up to 14.0 wt % after 8 hours reaction. It was found that 2-Ethylhexyl glycidyl ether which contains aliphatic moiety was very effective compound for eliminating the primary aromatic amine compound :md the optimal mole ratio of 2-ethylhexyl glycidyl ether to MAD was 3. The final polyol after deamination by 2-ethylhexyl glycidyl ether has an appropriate viscosity(less than 500 centi poise) for polyurethane reaction.

• Journal of Food Hygiene and Safety
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• v.30 no.1
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• pp.81-86
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• 2015

The purpose of our paper was to investigate the migration level of 4,4'-MDA(4,4'-methylenedianiline), 2,4-TDA(2,4-toluenediamine), aniline, acrylonitrile and methylmeth acrylate from plastic cookwares into food simulants and to evaluate the safety of each monomers. The test articles for monomers were PA (polyamide) items for 4,4'-MDA, 2,4-TDA and aniline, PU (polyurethane) items for 4,4'-MDA, ABS (acrylonitrile-butadiene- styrene) items for acrylonitrile, and acrylic resin items for methylmethacrylate. All the article samples of 321 intended for contact with foods were purchased in domestic market. 4,4'-MDA, 2,4-TDA and aniline were analyzed by LC-MS/MS (liquid chromatography -tandem mass spectrometer), acrylonitrile by GC-NPD (gas chromatography-nitrogen phos phorus detector) and methyl methacrylate by GC-FID (gas chromatography-flame ionization detector). The migration level of monomers were within the migration limits of Ministry of Food and Drug Safety (MFDS). As a result of safety evaluation, our results showed that the estimated daily intake (EDI, mg/kg bw/day)s were $2.39{\times}10^{-9}$ and $1.20{\times}10^{-9}$ for 4,4'-MDA and 2,4-TDA of PA, $4.32{\times}10^{-9}$ for acrylonitrile of ABS and $2.27{\times}10^{-7}$ for methylmethacrylate of acrylic resin. Reference Dose (RfD, mg/kg bw/day) of acrylonitrile and tolerable daily intake (TDI, mg/kg bw/day) of methacrylate were established respectively as 0.001 by EPA (US Environmental Protection Agency) and as 1.2 by WHO (World Health Organization). When comparing with RfD and TDI, the EDIs of acrylonitrile and methylmethacrylate accounted for $4.32{\times}10^{-4}%$ and $1.89{\times}10^{-5}%$ respectively.

• Applied Chemistry for Engineering
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• v.9 no.1
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• pp.13-19
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• 1998

Copolyimide membranes of different chemical structure based on pyromellitic dianhydride (PMDA)/methylendianiline(MDA) were prepared by varying their chemical compositions with adding meta-phenylendiamine (MPD), para- phenylendiamine (PPD), 2,4,6- trimethyl-1,3-phenylenediamine(TriMeMPD) as a co-monomer. The $N_2$ and $O_2$ permeation properties are qualitatively correlated to specific free volume and intersegmental distance of membrane. The partial replacement of MDA with MPD or PPD caused in the PMDA/MDA based membranes increase in density, and decrease in free volume, d-spacing, consequently resulted in decreased permeability coefficient. In the case of TriMeMPD, opposite results were observed. In all membranes, the permeability coefficients were pressure independent, and membranes which have high permeability coefficient showed low $N_2/O_2$ ideal separation factor as an usual manner. The permeability coefficient also increased with temperature and $N_2/O_2$ ideal separation factor decreased. The increase ratio of the $N_2$ permeability coefficient was larger than that of $O_2$.