• 폴리머
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• 제27권3호
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• pp.169-175
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• 2003

무독성의 반응형 난연 도료를 제조할 목적으로 모체수지 1개의 구조단위 속에 2개의 인산기를 보유한 파이로포스포릭 락톤 변성 폴리에스터 (PATT)를 합성하고, PATT에 이소시아네이트인 toluene diisocyanate-isocyanurate를 상온경화시켜 2성분계 폴리우레탄 난연 도료(PIPUC)를 제조하였다. PIPUC로서 도막제작 후 비난연 도료와의 도막물성을 비교한 결과 난연 성분 도입에 따른 난연 도료의 물성이 저하되지 않음을 알았다. 난연성 시험 중 45$^{\circ}$ Meckel burner 법에서는 탄화길이가 3.1~4.4 cm를, LOI법에서는 LOI 27~30%를 각각 나타냄으로써 양호한 난연 효과를 보여주었고, SEM에 의한 표면 도막을 관찰한 결과 도막의 결함이나 상분리 현상이 생기지 않음을 관찰하였다.

• 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.

• Fibers and Polymers
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• 제2권3호
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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.

• 분석과학
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• 제18권6호
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• pp.511-519
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• 2005

식품 포장재에 사용되는 접착제의 원료로 사용되는 우레탄의 주원료인 톨루엔 디이소시아네이트(TDI)는 인체에 노출될 경우에 독성을 일으킬 수 있다. GC/MS를 사용하여 식품 포장재에 잔류하는 TDI를 분석하기 위한 시료 전처리 조건과 분석조건을 확립하였다. 포장재 중에 포함된 TDI는 n-헵탄, 4%아세트산 등과 같은 식품유사용매를 사용하여 추출된 후, 기체 크로마토그래프/질량분석기 (GC/MS)에 의해 분석되었다. 26개의 식품 포장재를 측정한 결과 10개의 시료에서 $0.51{\sim}60.88{\mu}g/ml$ 농도 범위에서 TDI가 검출되었다. 포장재의 절단된 면에 대한 추출 용매의 접촉을 피하고 포장재 면만이 접촉하도록 한 후 추출시간을 달리하면서 실험한 결과 2시간 추출 조건에서도 0.7% 수준으로 감소되어 실제 식품 조리시에 TDI가 다량 검출될 위험은 미미한 것으로 평가되었다. 본 연구에서 확립된 톨루엔 디이소시아네이트에 대한 분석법은 외국의 유해물질에 대한 관리기준을 만족시키는 정량한계를 확보한 신뢰성 있는 방법으로 추후 관련 연구를 위한 기초 분석기술로 활용도가 높을 것으로 예상된다.

• Macromolecular Research
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• 제13권5호
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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.

• 한국산업보건학회지
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• 제23권2호
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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.

• Elastomers and Composites
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• 제49권1호
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• pp.31-36
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• 2014

Sebacic acid, isophthalic acid, ethylene glycol, neopentyl glycol를 각각 1몰씩 사용하여 폴리에스터 폴리올을 합성하였다. 합성된 폴리올의 수산기가는 56.6 mg KOH/g이고 분자량은 1,980 g/mole 이었다. 합성한 폴리에스터 폴리올에 toluene diisocyanate와 쇄연장제로 ethylene glycol, 1,4-butandiol, 1,2-propylene glycol을 각각 넣고 폴리우레탄을 합성하였다. GPC로 측정한 3 가지 폴리우레탄의 분자량은 각각 5850, 6160, 6480 g/mole 이었다. FT-IR에 의한 구조분석에서 폴리에스터 폴리올은 3600 $cm^{-1}$ 부근에서 -OH 기가 관찰되었고, 2950 $cm^{-1}$ 에서 sebacic acid의 -CH shoulder가 나타났으며, ester의 carbonyl group은 1730 $cm^{-1}$ 부근에서 나타났고, isophthalic acid의 benzene ring은 1600 $cm^{-1}$, 740 $cm^{-1}$에 관찰되었다. 폴리우레탄의 -OH 피크가 3600 $cm^{-1}$ 에서 나타났고, 3300 $cm^{-1}$ 부근과 1530 $cm^{-1}$ 에서 우레탄기 중의 -NH 기를 확인할 수 있었다. $^1H$ NMR에 의한 구조분석에서 폴리에스터 폴리올은 sebacic acid는 1.3, 1.5, 2.1 ppm에서, isophthalic acid는 7.3, 8.1, 8.7 ppm에서, ethylene glycol은 4.2 ppm에서, neopentyl glycol은 0.8, 3.2, 3.9 ppm에서 관찰되었다. 폴리우레탄의 경우에는 폴리에스터 폴리올과 유사하나 toluene diisocyanate의 도입에 의한 벤젠고리의 피크가 7 ppm에서 미약하게 나타났다.

• 폴리머
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• 제37권2호
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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.

• 한국염색가공학회:학술대회논문집
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• 한국염색가공학회 2008년도 제39차 학술발표회
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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.

• Toxicological Research
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• 제19권2호
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• pp.133-139
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• 2003

Allergic contact dermatitis may be caused by a wide variety of chemicals. A murine local lymph node assay (LLNA) has been developed as an alternative to guinea pig models for assessing the contact sensitization potential of chemical. However, there is a need to develop a nonradioisotopic endpoint for the LLNA, because of the radioisotopic method's requiring the use of special facilities. In this study, we investigated the development of a nonradioisotopic endpoint for LLNA using ELISA (enzyme-linked immunosorbent assay). Female Balb/c mice were treated by the topical application on the dorsum of both ears with four different strong sensitizers, 2,4-dinitrochlorobenzene (DNCB), oxazolone (OXZ), toluene diisocyanate (TDI), and trimellitic anhydride (TMA), and a strong irritant, sodium lauryl sulfate (SLS), once daily for three consecutive days. The proliferation of cells in the auricular Iymph node was analyzed by means of the labelling index (Ll) of bromodeoxyuridine (BrdU) incorporation into cells. The weights of the Iymph nodes in the mice treated with allergens, DNCB, OXZ, TDl and TMA were increased compared to the vehicle control. The stimulation index (Sl) of mice treated with DNCB, OXZ, TDl, and TMA was over three-fold increase compared to the vehicle control. However, the S1 of mice exposed to SLS was not significantly increased compared to the vehicle control, while the lymph node weight of SLS was significantly increased. These results suggest that the LLNA modified endpoint using ELISA based on BrdU incorporation could provide a useful method of screening for irritants and allergens.