• 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.

• 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 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.

• 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 $O_2$.

• 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.

• 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.

• 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.

• 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.