• Analytical Science and Technology
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• v.18 no.6
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• pp.511-519
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• 2005

A method for determination of toluene diisocyanates (TDI) in toluene diisocynate (TDI)-based polyurethane (PUR) packing material was investigated, and also the migration of TDI to food was studied. TDI was extracted using food simulants such as n-haptane and 4% aqueous acetic acid. The determinations were performed using gas chromatography/mass spectrometry (GC/MS). One of major components for polyurethane, toluene diisocyanates, were detected in ten samples among twenty six food contact materials with the concentration range of $0.51{\sim}60.88{\mu}g/ml$. However the highest extracted amount was just 0.7% of $60.88{\mu}g/ml$ if the contact surface of food packing for extracting liquid was limited to the outer layer without exposure of the cutting edge of food packing multi-layers. The result of this study and the analysis method for TDI diisocyanate will be very useful for further study about food contact material, and the monitoring result could be used for evaluating the safety of food contact material before it is to be used for food, preservation.

• Macromolecular Research
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• v.16 no.3
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• pp.194-199
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• 2008

Four novel polyurethanes were prepared from 4-{(4-hydroxyphenyl)iminomethyl} phenol by reactions with two aromatic diisocyanates, 4,4'-diphenylmethane diisocyanate and toluene 2,4-diisocyanate, and two aliphatic diisocyanates, isophorone diisocyanate and hexamethylene diisocyanate. The polyurethanes formed were characterized by UV-vis, fluorescence, FT-IR, $^1H$-NMR, $^{13}C$-NMR, differential scanning calorimetry, thermogravimetry, and X-ray diffraction. The polymers were semi-crystalline and all polymers were soluble in polar aprotic solvents.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.30 no.2
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• pp.134-152
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• 2020

Objectives: The objective of this study was to evaluate volatile organic compounds (VOCs) and toluene diisocyanates (TDIs) exposure among polyurethane waterproofing workers in the construction industry. Methods: Task-based personal air samplings were carried out at seven construction sites using organic vapor monitor for VOCs (n=88) and glass fiber filters coated with 1-(2-pyridyl)piperazine(1-2PP) for TDIs (n=81). The concentration of VOCs and TDIs were shown for four different work types(mixing paint, primer roller painting, urethane resin spread painting, painter assistant) at five different worksites (rooftop, ground parking lot, piloti, bathroom, and swimming pool). The two TDI sampling methods (filter vs impinger) were evaluated in parallel to compare the concentrations. Results: The geometric mean(GM) concentration of VOCs Exposure Index (EI) was highest for primer roller painting (1.4), followed in order by, urethane resin spread painting (0.85), mixing paint (0.53), and painter assistant (0.35) by work types. The GM of VOCs EI was highest for bathroom (1.4) followed in order by, swimming pool (0.85), piloti (0.89), ground parking lot (0.82) and rooftop (0.57) by worksites. The GM of 2,4-/2,6-TDI concentration was 0.052 ppb and 0.432 ppb each. There was no statistical difference in TDIs concentrations among worksites. The concentration of 2,6-TDI was ten times higher than that of 2,4-TDI. The concentration of 2,6-TDI by impinger method was 5.7 times higher than that by filter method. Conclusions: In this study, we found 38.6% of the VOCs samples exceeded the occupational exposure limits and 19.8% of the 2,6-TDI samples exceeded 1 ppb among polyurethane waterproofing workers. The most important determinants that increase the concentration of VOCs and TDIs was indoor environment and primer painting work.

• 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.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.9 no.1
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• pp.156-172
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• 1999

Potential chemical hazards encountered in painting operation of four shipyards and a ship-repair shop were investigated through the material safety data sheets (MSDS). Material safety data sheets (MSDS) for 307 paints, 50 thinners and 34 binders were collected and reviewed. It was shown that various organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, ketones, alcohols, glycols, glycol ether acetates and esters were contained in painting materials. Of these solvents, xylene was found in the largest number of painting materials. sixty percent of the thinners contained xylene in the contents of 20-100%. Other most frequently found solvents were 1-methoxypropanol, 1-methoxypropyl acetate, n-butanol, methyl isobutyl ketone, toluene, isopropanol, and n-butyl acetate, etc. Glycol ethers such as 2-methoxyethanol (2-ME), 2-methoxyethyl acetate (2-MEA), 2-ethoxyethanol (2-EE), 2-ethoxyethyl acetate (2-EEA) and 2-butoxyethanol (2-BA) were regarded as having the potential to cause adverse reproductive effects, embryotoxic effect and hematotoxic effects, and were found in some epoxy panting materials. Coal tar pitch was included in some paints(13%) where polynuclear aromatic hydrocarbons (PAHs) could be contaminated. Inorganic pigments such as lead chromate and zinc potassium chromate were found in some paints (8%). The epoxy resin based paints, which may contain isocyanates such as toluene diisocyanates and hexamethylene diisocyanates causing potential sensitization and asthma to upper respiratory organ, were mostly used in the shipyards. The constituents in the MSDS were significantly different from the results analyzed using gas chromatography/mass detector: minor constituents or impurities were omitted in many MSDS. In conclusion, xylene was the most frequent organic solvent in painting materials, and glycol ethers, including 2-ME, 2-MEA, 2-EE, 2-EEA and 2-BA, were found some products. Also, painting workers may be exposed to PAHs, lead, chromate, isocyanates, organic tin and other various chemicals. The compositions of chemicals in painting materials were variable significantly, and the hazards were changed. These facts should be considered in environmental monitoring and control of the hazards.

• Fibers and Polymers
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• v.2 no.3
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• pp.122-128
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• 2001

UV-curable polyurethane acrylate prepolymers were prepared from diisocyanates [isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI), or 4,4'-dicyclohexylmethane diisocyanate (H$_{12}$MDI)], diols [ethylene glycol (EG), 1,4-butane diol (BD), or 1,6-hexane diol (HD)], polypropylene glycol as a polyol. UY-curable mixtures were formulated from the prepolymer (90 wt%), reactive diluent monomer trimethylol propane triacrylate (10 wt%). and photoinitiator 1-hydroxycy-clohexyl ketone (3 wt% based on prepolymer/diluent). The effects of different diisocyanates/low molecular weigh dial on the dynamic mechanical thermal properties and elastic recovery of UV-cured polyurethane acrylate films were examined. The tensile storage modulus increased a little in the order of EG > BD > HD at the same diisocyanate. Two loss modulus peaks for all samples are observed owing to the glads transition of softs segments ($T_gh$) and the glass transition temperature of hard segments ($T_gh$). For the same diisocyanate, $T_gh$, decreased, however, $T_gh$ increased, in the order of HD > BD > EG. The elastic recovery also increased in the order of HD > BD > EG at the same diisocyanate. In case of same diols, $T_gh$ increased in the order of $H_12$MDl > TDI > IPDI significantly. The ultimate elongation and elastic recovery increased in the order of TDI > IPDI > $H_12$MDl at the same diol.l.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.23 no.2
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• pp.95-102
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• 2013

Objectives: The aim of this study is to present an appropriate sampling method for individual exposure assessment based on a comparison of toluene diisocyanate (TDI) concentrations collected through different sampling methods by work process type. Methods: Two plants handling TDIs in the Incheon area were selected. The samplings were taken during respective processes of spray painting, drying, grinding, and foaming, in which the production of TDIs took on different forms. For the sampling methods for airborne TDIs, open-face cassette holder, modified 2-piece cassette holder, and impinger were used, and the sampling was performed simultaneously at the same locations. Results: The comparison of TDI collection concentrations by each process depending on the sampling method showed high concentrations in the order of the impinger, modified 2-piece cassette holder, and open-face cassette holder for spray painting and foaming. In all processes with the exception of drying, TDI collection concentrations were higher for sampling done with the modified 2-piece cassette holder than with the open-face cassette holder. Conclusions: Based on these results, the modified 2-piece cassette holder was found to be a more appropriate sampling method than the open-face cassette holder when taking individual samples of TDIs from spray painting, grinding, and foaming processes. In particular, for individual exposure assessment of the spray painting process, which features comparatively high collection concentrations compared to the other processes, the use of a modified 2-piece cassette holder is considered appropriate.

• Polymer(Korea)
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• v.25 no.1
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• pp.33-40
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• 2001

Fluorinated polyurethane elastomers were synthesized by two step polyaddition of a perfluorinated polyether diol(trade name of Fomblin $ZDOL^{\circledR}$) and diisocyanates such as 4,4'-diphenyl methane diisocyanate(MDI) and toluene 2,4-diisocyanate(TDI). In order to control the Fomblin moiety of the soft segment in the synthesized elastomers to 10~50%, polyether type polyols such as polypropylene glycol(PPG) and polytetramethylene glycol(PTMG) were mixed during the polymerization reaction. Ethylene diamine or 1,4-butane diol was used as chain extenders. The structure and average molecular weight of the produced polyurethanes were confirmed by using FT-IR, $^1H-NMR$, DSC, and GPC. The surface properties were analyzed by using X-ray photoelectron spectroscopy(XPS) and contact angle meter. From the results of the surface analysis it was concluded that the fluorine groups were localized on the surface rather than the inside of the polyurethane films.

• Macromolecular Research
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• v.13 no.5
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• pp.427-434
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• 2005

To improve the performance and reduce raw material costs, blocked isocyanates were prepared with mixture of blocking agents in many industries. Three blocked isocyanates (adducts) namely $\varepsilon$-caprolactam/benzotriazole-blocked 4,4'-diphenylmethane diisocyanate (MDI), toluene-2,4-diisocyanate (TDI) and 4,4'-dicyclohexyl-methane diisocyanate ($H_{12}$MDI) were synthesized. Six reference adducts were also prepared by blocking MDI, TDI, and $H_{12}$MDI with $\varepsilon$-caprolactam ($\varepsilon$-CL) or benzotriazole. The reactions were carried out in acetone medium and dibutyltin dilaurate (DBTDL) was used as a catalyst. The progress of the blocking reaction was monitored by IR spectroscopy. De-blocking temperatures (dissociation temperatures) of these adducts were studied using DSC and TGA and the results were correlated. As expected, the thermal analysis data showed that de-blocking temperature of blocked aromatic isocyanates was lower than that of the blocked aliphatic isocyanates. The low de-blocking temperature of blocked aromatic isocyanate could be due to electron withdrawing benzene ring present in the blocked isocyanates. It was also found that benzotriazole-blocked adducts de-blocked at higher temperature compared with $\varepsilon$-CL-blocked adducts.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.58-65
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• 1983

The mechanical properties (tensile strength, 100% modulus and hardness) of the urethane elastomers prepared from hydroxyl terminated polybutadiene (HTPB), several low molecular weight diols (ethylene glycol, 1, 3-propane diol, 1,4-butane diol, 1,5-pentane diol and 1,6-hexane diol) and two kinds of diisocyanates(TDI: toluene diisocyanate, IPDI: isophorone diisomechanical properties were enhanced for the increases of the concentrations of the urethane group, as predicted. In case of TDI, when the mechanical properties of the elastomers were plotted patterns were observed, which can be explained by hydrogen bondings depending on the number of the methylene carbons. But the mechanical properties of the elastomers derived from IPDI had decreasing curves against the number of methylene carbons in low molecular weight diols, without the characteristic zigzag patterns.