• 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.

• Textile Coloration and Finishing
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• v.29 no.1
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• pp.25-36
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• 2017

This study worked on the synthesis of waterborne polyurethane/epoxy hybrid resins containing aminosilane compound to replace conventional phenol resins used for a coating material for loudspeaker dampers, which are not harmful to human being. Waterborne polyurethane resins were synthesized from two diisocyanate of 4,4'-diphenylethane diisocyanate and toluene diisocyanate, two polyols of polyester polyols(PEP), polycarbonatediol(PCD), including and anionic center of dimethylol butanoic acid, a chain extenders of ethylenediamine(EDA), and a neutral agent of triethylamine. Synthesized polyurethane resins and commercially available bisphenol A type waterborne epoxy resin were blended in weight ratios of 80:20 to prepare polyurethane/epoxy hybrid resins. The synthesized waterborne polyurethane/epoxy hybrid resins were reacted with aminosilane compound to improve mechanical properties. Aminosilane-treated polyurethane /epoxy hybrid resins showed better mechanical properties.

• Polymer(Korea)
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• v.37 no.2
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• pp.232-239
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• 2013

A series of novel imidazole-blocked diisocyanate bioadhesives (IBAs) were synthesized from reaction of toluene 2, 4-diisocyanate (TDI), isophorone diisocyanate (IPDI), hydroxyl-terminated polylactide (HO-PLA-OH), 1,1,1-trimethylolpropane (TMP), and imidazole. Synthesis of IBAs was confirmed by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) revealed that the TDI-based IBA had lower thermal dissociation temperature and a faster deblocking rate than IBA based on IPDI. Hydroxyl-terminated polyurethane (HPU) was introduced to study the adhesive effect of the synthesized IBAs. Improvement on elastic modulus, tensile strength and water resistance of IBA-modified HPU in comparison with neat HPU suggested the good adhesive effect of IBA due to the strong chemical reaction between released NCO groups from IBA and hydroxyl groups from HPU.

• 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.

• IMMUNE NETWORK
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• v.2 no.3
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• pp.158-165
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• 2002

Background: Toluene diisocyanate (TDI) can cause contact allergy and occupational asthma, but the mechanism underlying sensitization to this chemical compound remains controversal. Also the correlation of mast cell with contact hypersensitivity (CHS) and the role of mast cell in the TDI-induced CHS is unknown. This issue was investigated by administrating TDI on the skin of genetically mast cell-deficient WBB6F1/$J-Kit^{W}/Kit^{W-v}$ ($W/W^{V}$) and congenic normal WBB6F1/J-Kit+/+ (+/+) mice. Methods: To development of animal model of TDI-induced CHS and to investigate the correlation of mast cell with CHS and the role of mast cell in the TDI-induced CHS, $W/W^V$ and +/+ mice were sensitized with TDI on the back skin at day 1 and day 8, and then challenged with 1% TDI on the ear at day 15. At 1, 2, 4, 8, and 24 hours after 1% TDI challenge, the ear thicknesses were measured. It was investigated the histologic changes of dermis in the ear of $W/W^V$ and +/+ mice at 24 hours after 1% TDI challenge. Results: TDI induced a significant ear swelling response in $W/W^V$ and +/+ mice. TDI induced the significant infiltrations of polymorphonuclear leukocytes and eosinophils in $W/W^V$ and +/+ mice, but not of mast cells in normal mice. And TDI increased a characteristic extent of mast cell degranulation in normal mice. There were no significant differences in the ear swelling and the infiltrations of polymorphonuclear leukocytes and eosinophils of normal versus $W/W^V$ mice, either at baseline or after TDI-induced CHS. Conclusion: From the above results, TDI can be used as a murine CHS model, and the mast cells may not be essential in TDI-induced CHS.

• Elastomers and Composites
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• v.49 no.1
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• pp.31-36
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• 2014

Polyester polyols were synthesized by using each one mole of sebacic acid, isophthalic acid, ethylene glycol, and neopentyl glycol. The synthesized polyol had 56.6 mg KOH/g of hydroxy value and 1980 g/mole of molecular weight. From FT-IR structure analysis of polyester polyol, Hydroxy group(-OH) was observed around 3600 $cm^{-1}$, -CH shoulder of sebacic acid at 2950 $cm^{-1}$, carbony group of ester around 1730 $cm^{-1}$, and benzene ring of isophthalic ring was represented at 1600 $cm^{-1}$, 740 $cm^{-1}$. In case of polyurethane, hydroxy peak was showed at 3600 $cm^{-1}$, and -NH group around 3300 $cm^{-1}$, 1530 $cm^{-1}$. From $^1H$ NMR measurement of polyester polyol, it was found that sebacic acid was represented at 1.3, 1.5, 2.1 ppm, isophthalic acid at 7.3, 8.1, 8.7 ppm, ethylene glycol at 4.2 ppm, and neopentyl glycol at 0.8, 3.2, 3.9 ppm, respectively. In the polyurethane, it is almost the same as spectrum of polyester polyol, but showed very week peak at 7 ppm by benzene ring of toluene diisocyanate.

• Journal of the Korean Applied Science and Technology
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• v.30 no.2
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• pp.305-311
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• 2013

PLA(polylactic acid), one of biodegradable polymers was blended with various amounts of wood pulp powder through solution blending technic to verify the effect of reinforcing pulp amount on the mechanical properties of blend films. Also these blend films were further modified with TDI(toluene diisocyanate) as crosslinking agent to introduce urethane functions by reaction of pulp hydroxyl groups and isocyanate. As a result, the tensile strength of blend film with 0.25 wt% pulp was increased from $565.25kg_f/cm^2$ for PLA film itself to $624.20kg_f/cm^2$. However, elongation of this film was decreased by 50% of that of PLA film itself. Only PLA/pulp blend film further modified with 500% of TDI/0.25 wt% pulp showed the slightly increased tensile strength but decreased elongation. Melting point and glass transition temperature of PLA/pulp blend films were confirmed by using Differential Scanning Calorimeter(DSC). Thermal stability of these blend films measured by TGA showed only a slight increase at temperature lower than $300^{\circ}C$.

• 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.

• Proceedings of the Korean Society of Dyers and Finishers Conference
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• 2008.10a
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• pp.9-10
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• 2008

Tricrecyl phosphate(TCP)-containing polyurea microcapsules were prepared by interfacial polymerization using aromatic 2,4-toluene diisocyanate(TDI) and Ethylene diamine(EDA) as wall forming materials. The effects of the protective colloids of polyvinylalcohol(PVA) and gelatin were investigated through experimentation.