• 한국산업보건학회지
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• 제23권4호
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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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• 제50권3호
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• pp.417-420
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• 2012

본 연구는 Pd/$SiO_2$ 촉매를 이용하여 2,4-dinitrotoluene(2,4-DNT)을 2,4-toluene diisocyanate(2,4-TDI)로 환원시키는 반응에 관한 연구이다. 반응 조건은 $200^{\circ}C$에서, 일산화탄소를 주입하여 100 bar에서 실험을 진행하였으며, 피리딘이 TDI의 수율에 미치는 영향에 대해 연구 하였다. 반응 실험 결과 피리딘을 넣지 않은 경우 TDI는 생성되지 않았고, 피리딘을 첨가하면 TDI가 생성되었다. 직접 카보닐화를 이용한 균질계상에서의 TDI 합성 연구 결과에 의하면 팔라듐과 피리딘의 착이온이 형성되어 촉매작용을 하는 것으로 알려져 있다. 피리딘을 첨가하였을 경우 TDI가 합성되는 것이 팔라듐 용출에 의한 것인지 확인하기 위해 ICP-AES 분석을 시행하였다. 20 vol% 피리딘을 첨가한 반응에서 반응 후 촉매의 팔라듐 함량이 반응 전에 비해 52% 감소하였다. 이러한 결과는 피리딘을 첨가한 반응실험에서 용출된 팔라듐이 피리딘과 착이온을 형성하는 과정을 거쳐 TDI가 생성되는 것으로 설명될 수 있다.

• 한국산업보건학회지
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• 제16권3호
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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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• 제14권4호
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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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• 제44권3호
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• pp.329-335
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• 2009

4종류의 새로운 형태의 열방성 액정폴리우레탄을 4,4'-Bis(5-hydroxypentoxy)biphenyl (BP5)와 2,6-tolylene diisocyanate (2,6-TDI), 2,5-tolylene diisocyanate (2,5-TDI), 및 2,4-tolylene diisocyanate (2,4-TDI), 1,4-phenylene diisocyanate (1,4-PDI) 의 중부가 반응에 의해 합성하였다. 단량체 BP5은 스멕틱상을 형성하였으며 1,4-PDI/BP5을 제외한 나머지 폴리우레탄에서는 모두 액정성을 나타내었다. 생성된 폴리우레탄의 구조는 FT-IR과 ^1H$ NMR 스펙트럼으로 확인하였고 열적 성질은 DSC와 편광현미경으로 관찰하였다.

• 한국산업보건학회지
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• 제4권2호
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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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• 통권328호
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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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• 제48권5호
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• pp.615-620
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• 2010

본 실험은 다섯 종류의 새로운 형태의 액정성 폴리우레탄을 4,4'-Bis(3-hydroxypropoxy)biphenyl (BP3)와 2,6-tolylene diisocyanate(2,6-TDI), 2,5-tolylene diisocyanate(2,5-TDI), 2,4-tolylene diisocyanate(2,4-TDI), 1,4-phenylene diisocyanate(1,4-PDI) 및 hexamethylene diisocyanate(HDI)의 중부가 반응에 의해 합성하였다. 단량체 BP3은 스멕틱상을 형성하였으며 HDI/BP3을 제외한 나머지 폴리우레탄에서는 모두 단방성 액정성을 나타내었다. 그러나 메틸 치환기를 가지고 있지 않는 1,4-PDI/BP3에서는 DSC 및 편광현미경에서도 액정상을 전혀 관찰할 수 없었다. 합성된 화합물의 구조는 FT-IR 및 $^1H$-NMR에 의해 확인하였으며, 그들의 열적 상전이온도 및 안정성들은 DSC, 편광현미경 및 x-선 회절에 의해 조사하였다.

• Journal of Preventive Medicine and Public Health
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• 제47권1호
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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.

• 환경영향평가
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• 제28권2호
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• pp.169-182
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• 2019

낙동강 상류 수계에 위치한 영강, 내성천과 위천을 대상으로 2016년 5월부터 10월까지 부착돌말류를 이용한 생물학적 수질 평가를 하였다. 부착돌말류는 이동성이 없어 장기적인 수질상태를 반영할 수 있다. 채집된 부착돌말류는 총 158 분류군으로 2목 3아목 8과 34속 143종 15변종으로 구성되어 있다. 영강은 Achnanthes convergens 와 Achnanthes minutissima, 내성천은 Nitzschia inconspicua, 위천은 Achnanthes minutissima, Cocconeis placentula var. lineata와 Navicula minima가 우점하였다. CCA 분석 결과, 낙동강 상류 수계에서는 전기전도도, 총인과 총질소가 부착돌말류의 종조성에 중요한 요인들로 나타났다. 상관분석 결과, 부착돌말지수들(DAIpo 와 TDI)은 서로 높은 상관성(0.87)을 보였다. 부착돌말지수(DAIpo와 TDI)를 이용한 생물학적 수질평가 결과, 영강은 대부분의 지점에서 A등급으로 평가되었다. 내성천은 A등급으로 평가된 N1을 제외한 모든 지점에서 C~D등급으로 평가되었다. 위천은 W1의 DAIpo가 B~C등급이나 TDI는 D등급으로 평가되어, 이 지점의 생물학적 수질 평가는 DAIpo보다 TDI의 결과가 더 불량한 것으로 나타났다. W2의 DAIpo와 TDI는 A~D등급으로 수질의 변화가 심하였다. W3와 W4의 DAIpo와 TDI는 대부분 B와 C등급으로 각각 평가되었다.