• Toxicological Research
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• 제25권2호
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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.

• 한국환경보건학회지
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• 제49권6호
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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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• 제4권1호
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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.

• 한국산업보건학회지
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• 제26권2호
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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.

• 공업화학
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• 제9권1호
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• pp.13-19
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• 1998

Pyromellitic dianhydride(PMDA)와 methylenedianiline(MDA)을 기본으로 하고 이에 meta-phenylendiamine(MPD), para-phenylendiamine(PPD), 2,4,6-trimethyl-1,3-phenylenediamine(TriMeMPD)을 첨가하여 열적 이미드화법으로 서로 다른 화학적 구조를 갖는 폴리이미드 공중합체막을 합성하여 제조된 막들의 물성치들을 측정하고, 산소와 질소의 투과 특성을 막의 물성과 관련시켜 정성적으로 고찰하였다. PMDA-MDA막을 기준으로 PPD, MPD의 첨가는 막의 밀도를 증가시켰고, 이에 따라 막의 자유용적과 d-spacing 값의 감소를 나타내어 산소, 질소의 투과량을 감소시켰으며, TriMeMPD의 첨가는 반대의 경향을 나타내었다. 따라서 d-spacing값과 자유용적은 질소, 산소의 투과특성과 정성적 상관성을 가짐을 알 수 있었다. 모든 막에서 압력에 상관없이 투과 계수는 거의 일정한 값을 나타내었고, 막의 기체 투과계수가 증가하면 산소/질소의 이상분리인자는 감소하였다. 온도가 증가하면 투과량도 증가하였으며 이상분리인자는 감소하였으며, 질소 투과량의 상승비가 산소보다 더 크게 나타났다.

• 멤브레인
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• 제25권4호
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• pp.343-351
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• 2015

본 연구에서는 높은 기체선택도를 가지는 폴리이미드의 제조를 위해 2,2-bis(3,4-carboxylphenyl) hexafluoropropane과 두 종류의 아민인 2,4,6-Trimethyl-1,3-phenylenediamine (DAM)과 4,4-Methylenedianiline (p-MDA)을 이용하여 합성을 진행한 후 비용매 상전이법으로 비대칭 분리막을 제조하였다. 분리막 제조에 사용된 용매에 따른 물성변화를 확인하기 위하여 고분자 용액의 점도, 흐림점 측정을 통한 고분자의 상평형도, 비용매 상전이 계수 측정을 진행하였다. 상전이법을 이용하여 제조된 분리막은 SEM을 통해 용매 휘발시간에 변화에 따른 모폴로지를 확인하였고 이의 변화에 따른 기체 투과도 변화를 확인하였다. 기체투과도는 디메틸아세트아마이드를 사용하였을 때보다 N-메틸-2-피롤리돈을 사용하였을 때 $CH_4$, $N_2$, $O_2$, $CO_2$의 투과도와 각 기체에 대한 선택도가 높은 것을 확인하였다. 또한 용매 휘발 시간이 길수록 기체 투과도는 감소하지만 기체에 대한 선택도가 증가하는 것을 확인하였다.

• 한국재료학회지
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• 제11권9호
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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.

• 멤브레인
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• 제25권3호
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• pp.223-230
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• 2015

새로운 구조를 가진 공중합체 폴리이미드를 이용하여 고투과, 고선택성 기체 분리막을 제조하였다. 기체투과도와 용해도를 높이기 위해 무수물인 2,2-bis(3,4-carboxylphenyl) hexafluoropropane과 두 종류의 아민인 2,4,6-Trimethyl-1,3-phenylenediamine과 4,4-Methylenedianiline을 사용하여 신규 폴리이미드를 합성하였다. Triethylamine과 Acetic anhydride를 사용하여 화학적 이미드화 방법으로 공중합체를 합성하였으며, 평균분자량은 100,000 g/mol 이상을 나타내었다. 합성된 고분자의 열적 특성을 분석을 하기 위해 시차주사열량계(DSC)와 열중량분석기(TGA)로 측정을 하였으며, 유리전이온도(Tg)는 $300^{\circ}C$, 열분해 온도는 $500^{\circ}C$가 넘는 뛰어난 내열성을 나타내었다. 기체투과도 특성은 time-lag 장비를 사용하였으며 그 결과, 일반적인 폴리이미드의 경우 대부분 기체투과도가 1 barrer 이하의 수치를 보이지만, 합성된 고분자의 경우 산소투과도 10.10 barrer과 산소/질소 선택도의 경우 5.3으로 고투과, 고선택도를 나타내어 기체 분리막 분야에 적용 가능성을 확인할 수 있었다. 합성된 고분자 중 기체투과특성이 더 우수한 공중합 폴리이미드를 사용하여 중공사를 제조하였고, 이를 이용하여 기체투과특성을 측정하였다.

• 한국식품위생안전성학회지
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• 제30권1호
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• pp.81-86
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• 2015

국내 유통 중인 총 321건의 폴리아미드, 폴리우레탄, ABS, 아크릴 수지 재질 식품용 기구 중 이행우려가 있는 모노머인 4,4'-메틸렌디아닐린, 2,4-톨루엔디아민, 아닐린, 아크릴로니트릴 및 메틸메타크릴레이트에 대하여 이행량을 조사하고 안전성 평가를 실시하였다. 83건의 폴리아미드, ABS 및 아크릴 수지 재질 식품용 기구 검체에서 현행 식품용 기구 및 용기 포장 공전상의 용출규격 이하인 4,4'-메틸렌디아닐린, 2,4-톨루엔디아민, 아크릴로니트릴 및 메틸메타크릴레이트가 이행되었다. 이행량 결과를 토대로 안전성 평가 시나리오에 적용하여 4,4'-메틸렌디아닐린, 2,4-톨루엔디아민, 아크릴로니트릴 및 메틸메타크릴레이트의 EDI를 산출한 후 TDI와 비교하여 위해도를 평가하였다. EDI는 폴리아미드 재질 기구의 4,4'-메틸렌디아닐린과 2,4-톨루엔디아민의 경우 각각 $2.39{\times}10^{-9}$, 및 $1.20{\times}10^{-9}mg/kg\;bw/day$, ABS 재질 기구의 아크릴로니트릴의 경우 $4.32{\times}10^{-9}mg/kg\;bw/day$, 아크릴 수지 재질 기구 메틸메타크릴레이트의 경우 $2.27{\times}10^{-7}mg/kg\;bw/day$이었다. ABS 재질 기구 이행 아크릴로니트릴의 위해도는 RfD 대비 $4.32{\times}10^{-4}%$ 수준이었고, 아크릴 수지 재질 기구 이행 메틸메타크릴레이트의 위해도는 TDI 대비 $1.89{\times}10^{-5}%$ 수준이었다. 결론적으로 검토된 평가 항목들의 위해도는 TDI 대비 $4.32{\times}10^{-4}%$와 $1.89{\times}10^{-5}%$에 불과한 것으로 조사되어 안전한 수준인 것으로 사료되었다. 이러한 결과들은 앞으로 기구 및 용기 포장의 안전관리를 위한 과학적인 근거자료로 이용될 수 있을 것으로 판단된다.