• Journal of Korean Society of Occupational and Environmental Hygiene
• /
• v.9 no.2
• /
• pp.1-18
• /
• 1999

The purpose of this study was to compare performances of two analytical methods, the OSHA 42 and the NIOSH 5522, of quantifying total isocyanates in air. These methods were compared in terms of accuracy and precision and the detection limits using four(4) spiked samples in each of four(4) concentration levels which ranged from 0.25 to 2.0 times of the ACGIH TLV-TWA. In addition, two methods were used to as sess airborne concentrations of total isocyanates at the following processes including autobody spray painting, furniture spray painting, polyurethane foaming, urethane adhesion, UV coating, and pigment mixing. The results of this study showed that the NIOSH 5522 method was better than the OSHA 42 method in terms of accuracy, precis ion, and detection limit for quantifying airborne total isocyanates. It was also clear that the NIOSH method was capable of detecting not only monomeric but also non-monomeric isocyanates. The results of air concentrations of total isocyanates among processes studied indicate that some processes may exceed the recommended level of isocyanates. In addition, to evaluate toxicological effects of total isocyanates, it is recommended to consider additive effects of isocyanates present in mixtures.

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

• Journal of Preventive Medicine and Public Health
• /
• v.29 no.1 s.52
• /
• pp.103-112
• /
• 1996

We studied the association of nonspecific bronchial hyperresponsiveness with general characteristics, exposure concentration, respiratory symptoms, chest x-ray findings, past histories and pulmonary function. We determined bronchial hyperresponsiveness by methacholine challenge test. And we conducted a respiratory symptom questionnaire and performed spirometry on 111 workers occupationally exposed to isocyanates in various industries. About 21.6% of subjects had bronchial hyperresponsiveness. No significant differences were observed between the hyperresponsive and non-responsive group with respect to age, sex, employment period, height, and smoking histories. Cough and breathlessness were significantly associated with the bronchial hyperresponsiveness. The hyperresponsive group had more experience of bronchitis and asthma in the past than the non-responsive group. The lower $FEV_1\;and\;FEV_1%$ were closely related with bronchial hyperresponsiveness. Bronchial hyperresponsiveness seems to be associated with some of respiratory symptoms, past histories and pulmonary function parameters in workers exposed to isocyanates.

• Macromolecular Research
• /
• v.13 no.5
• /
• pp.427-434
• /
• 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 Adhesion and Interface
• /
• v.7 no.4
• /
• pp.53-59
• /
• 2006

The paper highlights technical advances and introduces recent innovations such as smart curing laminating adhesives for flexible packaging with low migration rates of aromatic isocyanates and amines. Latent reactive one-part systems on the basis of surface deactivated solid isocyanates open up new dimensions for heat setting adhesives and waterborne PU dispersions. The new generation of Purmelt Micro Emission adhesives contains less than 0.1% of MDI monomer, thereby drastically reducing the emission of hazardous isocyanate vapors during processing and setting a significantly improved technical standard in occupational safety. Once again, polyurethane adhesives have demonstrated their unique ability to adapt to new process, product, safety and environmental requirements.

• Journal of the Korean Chemical Society
• /
• v.17 no.3
• /
• pp.188-192
• /
• 1973

Reactions of trimethylsilylethylsulfide, trimethylsilylphenylsulfide, triethylstannylethylsulfide, and triethylstannylphenylsulfide with isocyanates were studied at various temperatures for 10 days. These Si-S and Sn-S bond compounds catalyzed the production of the cyclic dimer and trimer of phenylisocyanate, diphenylcarbodiimide and 1,3,5-triphenyl-4-phenyliminohexahydro-1,3,5-triazine-2,6-dione in the reaction of phenylisocyanate. In contrast, these compounds gave only the cyclic trimer, triethylisocyanurate, from ethylisocyanate.

• Journal of the Korean Chemical Society
• /
• v.15 no.6
• /
• pp.318-323
• /
• 1971

Reactions of trimethylsilyldiphenylphosphine with phenylisocyanate and ethylisocyanate were studied at various temperatures for 3 days. Trimethylsilyldiphenylphosphine gave cyclic dimer, cyclic trimer and diphenylcarbodiimide from phenylisocyanate, but gave cyclic trimer, triethylisocyanurate, only from ethylisocyanate. In these reactions, it is suggested that trimethylsilyldiphenylphosphine was used to be an effective catalyst for cyclization of isocyanates.

• YAKHAK HOEJI
• /
• v.36 no.5
• /
• pp.433-439
• /
• 1992

For the synthesis of tuberin derivatives, N-(disubstituted styryl) carboxamides, the series of cinnamic acids were transformed through chlorides, azides to isocyanates. And then isocyanates were reduced separately by Dibal and Grignard reagent. As a result of antimicrobial susceptibility test, N-(3,4-dichlorostyryl) formamide and N-(3,4-dichlorostyrl) acetamide showed comparatively large activity against some bacteria that is, MIC was respectively 50 ppm, $6.25{\sim}50\;ppm$. MIC of other derivatives was similiar to that of tuberin, about 100.

• Proceedings of the Korean Society of Sericultural Science Conference
• /
• 2002.10a
• /
• pp.96-96
• /
• 2002

No Abstract, See Full Text

• Journal of Environmental Health Sciences
• /
• v.22 no.2
• /
• pp.32-42
• /
• 1996

This study was performed to evaluate accuracy and precision of filter method and impinger method for analyzin airborne isocyanates in mixture (2, 6-TDI, HDI, 2, 4-TDI, MDI). Filter method was performed using the OSHA Method 42 and impinger method using the NIOSH Method 5521. The samples were analyzed by high performance liquid chromatography-ultraviolet detector (HPLC-UVD). After the optimum operating conditions for each method were investigated, samples with various concentration levels were quantified at the conditions. The precision was expressed by the pooled coefficient of variation(C.V.) and the accuracy by overall accuracy. The results are summarized as follows: 1. The optimum condition of filter method was determined at 35/65 ACN/buffer (0.01 M ammonium acetate) in mobile phase. And in case of impinger method, it was at 30/70 ACN/buffer(0.2 M sodium acetate). The effect of concentrations of acetate on the separation of the peaks was not significant, but, the effect of ACN/buffer ratio was significant. 2. The correlation coefficients for the two methods were above 0.9 in all isocyanate compounds. Average recovery efficiencies for 2, 6-TDI, HDI, 2, 4-TDI and MDI in filter method were 92.4%, 102.6%, 87.3% and 101.0%, respectively. Those in impinger method were 106.6%, 106.7%, 99.0% and 103.6%, respectively. As a result, the recovery efficiency of impinger method was higher than those of filter method in analyzing isocyanate compounds. 3. The pooled coefficients of variations of the methods were slightly higher than expected. The overall accuracies of the methods were within $\pm 25%$ for each isocyanate compound. Since these results satisfy NIOSH criteria, the accuracy of the experiment is appropriate. 4. As seen above, impinger method is more efficient than filter method. But, there are many disadvantages in impinger method. Therefore, solid sorbent such as a glass fiber filter must be developed in order to have the high efficiency not less than that of impinger method in the future.