• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.23 no.4
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• pp.341-347
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• 2013

Objectives: The aim of this study is to investigate the differences in airborne TDI concentrations based on the filter collection method and liquid collection method and to compare airborne TDIs concentrations by sampling method change when using the filter collection method in the spray-painting process. Methods: For the sample measurement, the filter collection method(OSHA#42) and liquid collection method(NIOSH#5522) were used; for the sampling method, the full-period single sampling and full-period consecutive sampling methods were used. The samples were collected in spray-painting and drying process locations. Results: In all samples collected from the spray-painting and drying process locations through the filter collection and liquid collection methods, greater amounts of 2,6-TDI than 2,4-TDI were detected. When the TDI collection concentrations based on the sampling methods were compared, the concentrations of 2,4-TDI and 2,6-TDI collected by the consecutive sampling method were higher than the concentrations of 2,4-TDI and 2,6-TDI collected by the single sampling method for both the filter collection method and liquid collection method used in the spray-painting process. These differences were statistically significant. Conclusions: When TDI collection concentrations based on the sample measurement methods were compared, the concentration of 2,4-TDI and 2,6-TDI collected through the liquid collection method were higher than the concentrations of 2,4-TDI and 2,6-TDI collected by the filter collection method, and the differences were statistically significant. In the drying process, no difference was shown in the collection concentrations of 2,4-TDI and 2,6-TDI with the two measurement methods.

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.417-420
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• 2012

This study is about reduction reaction making 2, 4-dinitrotoluene (2, 4-DNT) to 2, 4-toluene diisocyanate (2,4-TDI) with Pd/$SiO_2$. Catalytic systems based on Pd/$SiO_2$ at about $200^{\circ}C$ and under 100 bars of carbon monoxide. We studied the effect of pyridine on the yield of the TDI. TDI was not created without pyridine, but created with pyridine, at the reaction result. According to research, homogeneous synthesis of TDI with direct carbonylation, palladium and pyridine complexion is known to catalyze. When adding pyridine the reason of TDI synthesis is palladium leaching, ICP-AES was performed to confirm it. As a result, the proportion of Pd loaded in $SiO_2$ was decreased 52% than before, after the reaction by adding 20 vol% pyridine. Generating TDI by adding pyridine might be the effect of the complex ion, which is composed of leached palladium and pyridine.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.16 no.3
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• pp.222-232
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• 2006

Objectives: The objective of this study was to propose the total isocyanate analytical method which involves derivation of 2,4-toluene diisocyanate(2,4-TDI), 2,6-toluene diisocyanate(2,6-TDI), 4,4'-methylenediphenyl diisocyanate(4,4'-MDI) and 1,6-hexamethylene diisocyanate(1,6-HDI) using 2-chlorobenzyl alcohol(2-CBA) or 2,4-dichlorobenzyl alcohol(2,4-DCBA), and analyzing of hydrolysate of the synthesized urethane with the gas chromatography(GC)/flame ionization detector(FID), GC/pulsed discharge ionization detector-electron capture detector(PD-ECD) and GC/mass selective detector(MSD). Methods: Urethanes were synthesized by reacting 2,4-TDI, 2,6-TDI, 4,4'-MDI and 1,6-HDI to 2-CBA or 2,4-DCBA. Urethanes was verified by TLC, HPLC/UVD and GC/MSD. For field application, the most suitable condition that 2-CBA coated in glass fiber filter removed completely and urethanes were not removed was searched. 2-CBA generated from hydrolysis of urethanes according to hydrolysis conditions. Diisocyanates were collected on field air and analyzed. Results: Urethanes which were white and solid phase synthesized by reacting 2,4-TDI, 2,6-TDI, 4,4'-MDI, 1,6-HDI and 2-CBA or 2,4-DCBA. And urethanes were verified by TLC, HPLC/UVD and GC/MSD. The most suitable conditions to remove 2-CBA coated in glass fiber filter were $87^{\circ}C$ and 20 mmHg and urethanes were not removed under same condition. Hydrolysis yields of urethanes were 99 % to 111 %. 2-CBA, the hydrolysate of urethanes was analyzed by GC/FID, GC/PD-ECD and GC/MSD. Conclusions: Simultaneous analysis of 2,4-TDI, 2,6-TDI, 4,4'-MDI and 1,6-HDI deriving with 2-CBA and 2,4-DCBA, along with a total isocyanate analysis, was feasible with GC/FID, GC/PD-ECD and GC/MSD. This result will be a guide of further study on total isocyanate analysis.

• Toxicological Research
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• v.14 no.4
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• pp.525-533
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• 1998

The covalent interactions of toluenediisocyanate (TDI) with macromolecules were investigated both in vitro and in vivo. In vitro incubations of 2,4- and 2,6-TDI with DNA or proteins resulted in dose-dependent formation of TDI-protein and TDI-DNA adducts. TDI-treated DNA was highly resistant to enzymatic digestion and thermal hydrolysis, but was readily hydrolyzed under acidic conditions by releasing its corresponding toluenediamine (TDA), suggesting that TDI caused the crosslinking of DNA. Reaction of TDI with albumin and globin resulted in the formation of several adducts, and some adducts were formed in blood of TDI-treated rats in a dose-dependent fashion. Administration of TDI to rats resulted also in a dose-dependent binding of TDI to hepatic tissue. Levels of TDI-albumin adducts were 10 times higher than those of TDI-globin adducts; the biological half lives of TDI-albumin and TDI-globin adducts were 1.2 and 12.5 days, respectively. Globin adducts were detected up to 28 days after the treatment. Hepatic TDI protein adducts were persistent for a substantial period whereas the levels of hepatic TDI-DNA adduct were decreased rapidly. These results indicate that the isocyanato group of TDI is not readily hydrolyzed under physiological conditions, is transported to other organs, and is bound to DNA and/or proteins without further metabolic activation. As the adducted products degrade in the body, TDA is released and introduced to the liver. TDA may additionally bind to hepatic tissue after metabolic activation. Thus, the toxic effect of TDI exposure is considered to persist during the lifetime of the adducted biological macromolecules.

• Elastomers and Composites
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• v.44 no.3
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• pp.329-335
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• 2009

Four series of novel liquid crystalline polyurethanes were synthesized by the polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate (2,6-TDI), 2,5-tolylene diisocyanate (2,5-TDI), 2,4-tolylene diisocyanate (2,4-TDI), and 1,4-phenylene diisocyanate (1,4-PDI) with 4,4'-bis(5-hydroxypentoxy)biphenyl (BP5). 4,4'-bis(5-hydroxypentoxy)biphenyl exhibited a smectic type mesophase. Mesophase was found for all synthesized liquid crystalline polyurethanes except 1,4-PDI/BP5. The structures and the thermal properties of polyurethanes were studied by using FT-IR and ^1H$ NMR spectroscopy, DSC measurements and a polarizing microscope equipped with a heating stage.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.4 no.2
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• pp.137-147
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• 1994

This study was designed to identify and quantitate airborne isocyanate simultaneously by HPLC. These samples were collected using 1-(2-pyridyl)piperazine(1-2PP) coated glass fiber filter from polyurethane painting works at 8 wood furniture factories in Kimpo and Inchun. The results obtained were as follows : 1. The most suitable mobile phase condition of simultaneously analyzing isocyanates was 0.01 M ammonium acetate buffer ACN(70/30) adjusted to pH 6.2 from the beginning of the analysis to 20 min and 0.01 M ammonium acetate buffer/ACN(50/50) adjusted to pH 6.2 from 21 min to 40 min using the gradient mode. The peaks of isocyanates were able to obtain within 30 min. 2. The recovery efficiencies for 2,6-TDI, 2,4-TDI, HDI and MDI urea derivates spiked at the target concentration on coated glass fiber tillers were 91.00, 93.42, 91.31 and 94.21 %, respectively. 3. The qualitative analysis of the isocyanates samples from polyurethane spray painting works in wood furnture factories identified Ihree isocyanates, 2,6-TDI, 2,4-TDI and MOI. And their concentration ranges were 0-312.6, 0-56.3 and $0-62.1{\mu}g/m^3$, respectively. A disadvantage of using the colorimetric method for isocyanate analysis is its inability of separating isocyanates. This study identified such three isocyanates as 2,6-TDI, 2,4-TDI and MDI from polyurethane spray painting works in wood furniture factories. These isocyanates were successfully quantitated by HPLC by modifying the mobile phase condition and switching to gradient mode.

• 월간산업보건
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• s.328
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• pp.55-59
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• 2015

톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트 각각 또는 두 이성체 혼합물(TDI)에 대하여 TLV-TWA는 0.005 ppm, TLV-STEL은 0.02 ppm으로 직업적 노출기준을 권고하고 있다. 본 수치는 호흡기에 대한 영향과 과민성 반응에 대한 높은 발생 가능성을 최소화하기 위한 것이다. 산업현장에서 증기상 TDI 물질은 점막, 호흡기계에 심한 자극을 일으켜 천식과 같은 증후군 등 급성 발작을 유발한다. 고농도에 노출시 심한 기관지 경련, 폐렴, 폐부종, 두통, 불면증과 기관지염으로 이어질 수 있다. TDI에 상당 부분 노출되면 대부분의 사람들은 위와 같은 건강 영향을 경험하게 된다. 심지어 처음 노출되었을 경우에도 발생된다. TDI 노출 관련 연구자들은 일반 근로자들이 0.02 ppm 수준 정도로 가끔 노출되는 경우 건강 영향을 받지 않으나, 0.02 ppm이 무영향 수준으로 간주될 수 있는 그 어떠한 증거도 없다고 결론을 내렸다. TDI에 일단 감작되면 몇몇 근로자들은 노출 중단 후에도 몇 년 동안 건강 영향 증세가 지속된다. 따라서 감작제 표기는 호흡 노출을 통한 알레르기성 감작 증세의 명확한 증거로서 권고된다. A4(비발암성 물질) 표기는 생쥐와 흰쥐들을 대상으로 수행된 위장관 투여 연구와 흡입 연구들을 통해 얻어진 동물 노출 데이터에 근거하여 설정되었다. 불충분한 데이터로 피부 표기는 권고되지 않았다.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.615-620
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• 2010

In this study, five series of novel polyurethanes was synthesized by the polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate(2,6-TDI), 2,5-tolylene diisocyanate(2,5-TDI), 2,4-tolylene diisocyanate(2,4-TDI), and 1,4-phenylene diisocyanate(1,4-PDI), hexamethylene diisocyanate(HDI) with 4,4'-Bis(3-hydroxypropoxy)biphenyl (BP3), 4,4'-bis(3-hydroxypropoxy)biphenyl exhibited a smectic type mesophase. Monotropic mesophase was found for all synthesized liquid crystalline polyurethanes except HDI/BP3. In contrast, 1,4-PDI/BP3 without a methyl substituent in the phenylene unit exhibited no explicit mesomorphic behavior, which was confirmed by DSC and polarizing microscopy experiments. Structures of the compound were identified by FT-IR and $^1H$-NMR spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry(DSC), polarized optical microscopy(POM) and x-ray diffraction analysis.

• Journal of Preventive Medicine and Public Health
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• v.47 no.1
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• pp.57-63
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• 2014

Objectives: We established a Wistar rat model of asthma caused by toluene diisocyanate (TDI) exposure, and investigated the relationship between TDI exposure concentrations and respiratory hypersensitivity, airway inflammation, and cytokine secretions in animals, to better understand the mechanism of TDI induced occupational asthma. Methods: Wistar rats were exposed to two different concentrations of TDI vapor four hours a day for five consecutive days. Bronchoalveolar lavage (BAL) was performed, and differential leucocytes from the BAL fluid were analyzed. Lung histopathological examination was carried out to investigate the inflammatory status in the airways. Production of cytokines interleukin (IL)-4 and IL-5 productions in the BAL fluid in vivo was determined with enzyme-linked immunosorbent assay kits. Results: The TDI-exposed rats exhibited greater airway hypersensitivity symptoms than the control rats. The BAL differential cell count and lung histopathological examination demonstrated that inflammation reactions were present in both the central and peripheral airways, characterized with marked infiltration of eosinophils in the TDI-exposed rats. The cytokine assay showed that IL-4 and IL-5 were predominantly produced in the BAL fluid in vivo. Conclusions: These findings imply that TDI exposure concentrations may greatly affect the occurrence and extent of inflammatory events and that Th2 type cytokines may play an important role in the immunopathogenesis of TDI-induced occupational respiratory hypersensitivity.

• Journal of Environmental Impact Assessment
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• v.28 no.2
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• pp.169-182
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• 2019

This study assessed biological water quality using epilithic diatoms in the Yeong river, Naeseong stream and Wi stream in the upper region of the Nakdong river from May to October 2016. Epilithic diatoms were not mobile, so they could reflect long-term water quality. The sampled epilithic diatoms were identified a total 158 taxa which were composed to 2 orders, 3 suborders, 8 families, 34 genera, 143 species and 15 varieties. Dominant species were Achnanthes convergens and Achnanthes minutissima at Yeong river, Nitzschia inconspicua at Naeseong stream, and Achnanthes minutissima, Cocconeis placentula var. lineata and Navicula minima at Wi stream. As a result of the CCA, Electrical conductivity, total nitrogen and total phosphorus were important factors determining the diatom species composition in the upper region of the Nakdong river. The correlation between diatom indices (DAIpo & TDI) measured to be high in the correlation coefficient (0.87) from the result of correlation analysis. In the result of the assessment of biological water quality using DAIpo and TDI, Yeong river was rated as class A at most sites. Naeseong stream was rated as class C to D at all sites except for N1 which was rated as Class A. Wi stream was rated as class B to C for DAIpo of W1, and TDI was rated as class D. The assessment of biological water quality at this site showed inferior TDI result compared to that of DAIpo. DAIpo and TDI of W2 were rated as class A to D, and the water quality has changed a lot. W3 and W4 were mostly rated as class B and C respectively.