• Toxicological Research
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• v.25 no.2
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• pp.85-92
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• 2009

4,4'-Methylenedianiline (MDA) is an aromatic amine that is widely used in the industrial synthetic process. Genotoxic MDA forms DNA adducts in the liver and is known to induce liver damage in human and rats. To elucidate the molecular mechanisms associated with MDA-induced hepatotoxicity, we have identified genes differentially expressed by microarray approach. BALB/c male mice were treated once daily with MDA (20 mg/kg) up to 7 days via intraperitoneal injection (i.p.) and hepatic damages were revealed by histopathological observation and elevation of serum marker enzymes such as AST, ALT, ALP, cholesterol, DBIL, and TBIL. Microarray analysis showed that 952 genes were differentially expressed in the liver of MDA-treated mice and their biological functions and canonical pathways were further analyzed using Ingenuity Pathways Analysis (IPA). Toxicological functional analysis showed that genes related to hepatotoxicity such hyperplasia/hyperproliferation (Timp1), necrosis/cell death (Cd14, Mt1f, Timp1, and Pmaip1), hemorrhaging (Mt1f), cholestasis (Akr1c3, Hpx, and Slc10a2), and inflammation (Cd14 and Hpx) were differentially expressed in MDA-treated group. This gene expression profiling should be useful for elucidating the genetic events associated with aromatic amine-induced hepatotoxicity and for discovering the potential biomarkers for hepatotoxicity.

• Journal of Environmental Health Sciences
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• v.49 no.6
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• pp.334-343
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• 2023

Background: South Korea's Act on Registration and Evaluation, etc. of Chemicals (known as K-REACH) was established to protect public health and the environment from hazardous chemicals. 4,4'-Methylenedianiline (MDA), which is used as a major intermediate in industrial polymer production and as a vulcanizing agent in South Korea, is classified as a toxic substance under the K-REACH act. Although MDA poses potential ecological risks due to industrial emissions and hazards to aquatic ecosystems, no ecological risk assessment has been conducted. Objectives: The aim of this study is to assess the ecological risk of MDA by identifying the actual exposure status based on the K-REACH act. Methods: Various toxicity data were collected to establish predicted no effect concentrations (PNECs) for water, sediment, and soil. Using the SimpleBox Korea v2.0 model with domestic release statistical data and EU emission factors, predicted environmental concentrations (PECs) were derived for ten sites, each referring to an MDA-using company. Hazard quotient (HQ) was calculated by ratio of the PECs and PNECs to characterize the ecological risk posed by MDA. To validate the results of modeling-based assessment, concentration of MDA was measured using in-site freshwater samples (two to three samples per site). Results: PNECs for water, sediment, and soil were 0.000525 mg/L, 4.36 mg/kg dw, and 0.1 mg/kg dw, respectively. HQ for surface water and sediment at several company sites exceeded 1 due to modeling data showing markedly high PEC in each environmental compartment. However, in the results of validation using in-site surface water samples, MDA was not detected. Conclusions: Through an ecological risk assessment conducted in accordance with the K-REACH act, the risk level of MDA emitted into the environmental compartments in South Korea was found to be low.

• Analytical Science and Technology
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• v.25 no.4
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• pp.236-241
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• 2012

There are many industrial factories in the central Nakdong river basin and have been occurred water pollution accidents by hazardous chemicals such as phenol, 1,4-dioxane and perchlorate. In this study, ten compounds of semi-volatile organic compounds (SVOCs) (dichlorvos, toluene-2,4-diisocyanate, 4,4'-methylenedianiline, 4,4'-methylenebis (2-chloroaniline), diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthaltate, bis (2-ethylhexyl) adipate, benzophenone, 4,4'-bisphenol A) of hazardous chemicals which may be potentially discharged into the Nakdong river, were determined by gas chromatography-mass spectrometry (GC-MS) with disk-type solid-phase extraction. Accuracy and precision were in the range of 75.6~110.5%, and 4.6~12.7%, respectively and recovery was in the range of 72.4~127.9%. Three compounds (bis (2-ethylhexyl)adipate, benzophenone, 4,4'-bisphenol A) were detected in industrial wastewater such as wastewater treatment plants (WWTPs) and wastewater discharge facilities in the Nakdong River basin.

• Membrane Journal
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• v.25 no.4
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• pp.343-351
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• 2015

In this study, we synthesis polyimide with high gas selectivity using 2,2-bis(3,4-carboxylphenyl) hexafluoropropane, 2,4,6-Trimethyl-1,3-phenylenediamine (DAM) and 4,4-Methylenedianiline (p-MDA), and then the asymmetric membrane was fabricated by non-solvent phase separation method. To confirm the property change of the membrane using different solvent, we measured and compared the viscosity of the polymer solution, cloud point and non-solvent phase separation coefficient. The morphology and gas separation property of membrane prepared by phase separation method was confirmed using Field Emission Scanning Electron Microsope and the single gas permeation measurement apparatus. The single gas ($CH_4$, $N_2$, $O_2$, $CO_2$) permeation property and selectivity value of the membrane prepared with NMP was higher than the membrane prepared with DMAc. We confirmed that the gas selectivity of the membrane increased and the permeation property decreased with increasing of the solvent evaporation time.

• Membrane Journal
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• v.25 no.3
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• pp.223-230
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• 2015

We synthesized novel polyimides with high gas permeability and selectivity for application of gas separation membrane. 2,2-bis(3,4-carboxylphenyl) hexafluoropropane dianhydride (6FDA) and two kinds of amines with high permeability and solubility were used to prepare the novel polymide. 2,4,6-Trimethyl-1,3-phenylenediamine (DAM) was used to improve gas permeability and 4,4-Methylenedianiline was used to improve the gas selectivity respectively. The polyimide copolymers were synthesized by commercial chemical imidization method using Triethylamine and Acetic anhydride and their average molecular weights were over 100,000 g/mol. The glass temperature (Tg) and the thermal degradation temperature were characterized using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The synthesized copolymers showed high Tg over $300^{\circ}C$ and high thermal degradation temperature over $500^{\circ}C$. The gas permeation properties were measured by time-lag equipment. Although general polyimides showed very low gas permeability, synthesized polyimide copolymer showed high $O_2$ permeability of 10.1 barrer with high $O_2/N_2$ selectivity around 5.3. From this result, we confirm that these membranes have possibility to apply to gas separation membrane.

• Elastomers and Composites
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• v.51 no.2
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• pp.122-127
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• 2016

Thermal decomposition kinetics for two different types of polyurethane elastomers prepared with 2,2'-dichloro-4,4'-methylenedianiline (MOCA) and 3,5-dimethyl-thiotoluenediamine (Ethacure-300), based on PTMG/TDI isocyanate prepolymer, were studied using non-isothermal thermogravimetric analysis (TGA). Thermograms were obtained and analyzed using Friedman (FR) and Kissinger-Akahira-Sunose (KAS) methods for activation energy, $E_a$. The results obtained showed that decomposition reaction of both samples was observed similarly to occur through three different stages, i.e., initial stage with vaporization of low molecular weight materials, second stage of urethane linkage decompositions, and later stage of polyol segment decompositions. However, activation energy values at each stage for the sample cured with Ethacure-300 was much lower than those for the sample with MOCA, exhibiting relatively lower thermal stability for the sample with Ethacure-300 than that with MOCA.

• Elastomers and Composites
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• v.53 no.2
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• pp.52-56
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• 2018

The present study examines the transformation of dynamic DSC data into the equivalent isothermal data for the formation kinetics of a polyurethane elastomer. The reaction of 2'-dichloro-4,4'-methylenedianiline (MOCA) with a PTMG/TDI-based isocyanate prepolymer was evaluated. DSC measurement was performed in the dynamic scanning mode with several different heating rates to obtain the reaction thermograms. Then, the data was transformed into the isothermal data through a procedure based on Ozawa analysis. The main feature of this procedure was the transformation of $({\alpha}-T)_{\beta}$ curves from dynamic DSC into $({\alpha}-t)_T$ curves using the isoconversional $(t-T)_{\alpha}$ diagram. Validity was discussed for the relationship between the dynamic DSC data and the transformed isothermal results.

• Korean Journal of Materials Research
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• v.11 no.9
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• pp.786-791
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• 2001

$\alpha$,$\omega$-Bis(4-glycidyloxybenzylidene-4-aminophenyl)methane (BGBAM) was synthesized from the initial materials, 4-hydroxylbenzaldehyde (HBA), 4,4'-methylenedianiline (MDA) and epichlorohydrin. The DSC trace for BGBAM shows two endotherms associated with the liquid crystalline phase transition around $104.2^{\circ}C$ and the isotropic transition around $171.2^{\circ}C$, and it also has a broad exotherm in the range of $178~300^{\circ}C$ due to the anionic homopolymerization of BGBAM. DSC curve for the curing of BGBAM with hexamethylene diamine (HMD) shows an endothermic peak around $93^{\circ}C$ attributed to the melting of BGBAM. It also has three exothermic peaks around $128.4^{\circ}C$ and $180.2^{\circ}C$ associated with the epoxide-amine reaction and weak peak in the range of $200~263^{\circ}C$ related to the anionic homopolymerization between the unreacted epoxide groups. The activation energy values of cure reaction by Kissinger method are 66.5, 67.3 and 90.6 kJ/mol for $T_{pl},\; T_{p2}\; and \;T_{p3},\; respectively$. The kinetic parameters by isoconverional method are similar value to those from Kissinger method.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.26 no.2
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• pp.178-187
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• 2016

Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.

• Elastomers and Composites
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• v.50 no.2
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• pp.92-97
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• 2015

A study on reaction kinetics for a PTMG/TDI prepolymer with 2,2'-dichloro-4,4'-methylenedianiline (MOCA), of which formulations may be generally used for fabricating high performance polyurethane elastomers, was peformed using non-isothermal differential scanning calorimetry (DSC). A number of thermograms were obtained at several constant heating rates, and analysed using Flynn-Wall-Ozawa (FWO) isoconversional method for activation energy, $E_a$ and extended-Avrami equation for reaction order, n. Urea formation reaction of the present system was observed to occur through the simple exothermic reaction process in the temperature range of $100{\sim}130^{\circ}C$ for the heating rate of $3{\sim}7^{\circ}C/min$. and could be well-fitted with generalized sigmoid function. Though activation energy was nearly constant as $53.0{\pm}0.5kJ/mol$, it tended to increase a little at initial stage, but it decreases at later stage by the transformation into diffusion-controlled reaction due to the increased viscosity. Reaction order was evaluated as about 2.8, which was somewhat higher than the generally well-known $2^{nd}$ order values for the various urea reactions. Both the reaction order and reaction rate explicitly increased with temperature, which was considered as the indication of occurring the side reactions such as allophanate or biuret formation.