• Journal of the Korean Applied Science and Technology
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• v.27 no.4
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• pp.461-469
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• 2010

Polyurethane adhesive is used in various fields as flexible packaging materials including a food packaging field. Therefore, the purpose of this study is synthesis of polyurethane adhesive which uses aliphatic isocyanate, and compares with aromatic isocyanate. The isocyanates for this test are toluene-2,4-diisocyanate(TDI), hexamethylene diisocyanate(HDI), 4,4-dicyclohexyl ethane diisocyanate($H_{12}MDI$), and isophorone diisocyanate(IPDI). And, the effect of any other diisocyanate are evaluated by several methods as for curing rate test, accelerate weathering test, and peel strength test. The polyurethane adhesive using curing catalyst and HDI has adhesion strength of about 560 g/15 mm between aluminium foil and nylon, about 1,520 g/15 mm between nylon and CPP. Those parameters are similar to polyurethane adhesive with TDI. Also, in case of curing rate, those are similar to TDI type polyurethane adhesive. Moreover, data of ${\Delta}E$ as color variation by QUV tester is equal to 4.12, as 48% against those of TDI type.

• Environmental Analysis Health and Toxicology
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• v.15 no.1_2
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• pp.53-59
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• 2000

The purpose of this study is the development of the simple and precise determination method of ethyl isocyanate (EIC) and propyl isocyanate (PIC) through derivatization using secondary aliphatic amines by gas chromatography with flame ionization detector. The urea derivatives are quantitatively and simultaneously derived from EIC and PIC with secondary aliphatic amines such as dipropylamine, dibutylamine. and dipentylamine in methylene chloride, and confirmed by thin layer chromatography and gas chromatography with mass selective detector. For GC/FID, according to the increasing carbon atom of the amines, the retention time and peak area of the urea derivatives are increased. The instrumental detection limits for EIC and PIC were about 23.3∼34.8 $\mu\textrm{g}$ and 21.6∼28.9 $\mu\textrm{g}$, respectively.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.11 no.3
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• pp.249-253
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• 2001

The purpose of this study is the development of the simple and precise sampling and analysis method of methyl isocyanate(MIC) in the work place as their secondary aliphatic amine derivatives by gas chromatography with flame ionization detector. The urea derivatives are quantitatively and simultaneously derived from MIC with secondary aliphatic amines such as dipropylamine(DPA), dibutylamine(DBA), and dipentylamine (DAA) in methylene chloride. The method is based on sampling glass tube in XAD-2 resin which is coated with secondary aliphatic amines. The samples are desorbed by $2m{\ell}$ methylene chloride and analysed using gas chromatography with flame ionization detector(GC/FID). In the results, the detection limit of the overall procedure and reliable quantity are $0.020-0.027{\mu}g$($1.347-1.740{\mu}g/m^3$(0.529-0.684 ppb) based on a 15 L air volume) MIC per sample. The average desorption efficiencies are 97.96 - 101.23 %. The results of versus storage time are high and stable recovery rates.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.743-747
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• 1994

The catalytic effects of carboxylic acid and dibutyltin dilaurate(DBTL) on the curing rate of acrylic polyol with isocyanate prepolymer were investigated. In this work reaction of a biuret type aliphatic isocyanate with acrylic polyol follows the second order reaction in the thin film state. Carboxylic acid of acrylic polyol has a strong catalytic effect on the isocyanate groups and influences greatly on curing rate, also DBTL is more effective catalysis on acrylic polyol without carboxylic acid than with carboxylic acid.

• Polymer(Korea)
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• v.29 no.1
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• pp.59-63
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• 2005

Kinetic study of a reaction between poly(caprolactone diol) and aliphatic isocyanate was investigated by FTIR spectroscopy. The reaction rate was obtained from analyzing the absorbance change of NCO peak (2265 $cm^{-1}$) in series IR spectra. In the results, the overall reaction between PCL and isocyanate conformed to the simple second-order law, and the rate constant increases with increasing reaction temperature. The activation energies obtained from the evaluation of kinetic data were 25.4∼30.9 kJ/mol for hexamethylene diisocyanate and 16.8∼22.1 kJ/mol for cyclohexylmethane diisocyanate, respectively.

• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.258-265
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• 2009

An anionic polyurethane dispersions (PUDs) were synthesized from the poly (tetramethylene glycol) (PTMG, Mw = 2000 g/mol), mixed isocyanate of dicyclohexylmethane-4,4'-diisocyanate $(H_{12}-MDI)$ and 4,4'-diphenylmethane diisocyanate (MDI), and dimethylol propionic acid (DMPA) as anionic site, following a prepolymer mixing process. Triethylamine (TEA) was used as a neutralization agent and the ethylenediamine (EDA) as the chain extender of the prepolymer. The effects of the DMPA molar ratio and aromatic diisocyanate content in the mixed isocyanate on the particle size and viscosity of PUD were studied. Also, the mechanical and thermal properties of the PUD cast films were discussed according to the molar ratio of DMPA and aromatic isocyanate content. It was found that the particle size and the viscosity of an anionic PUD decreased with increasing DMPA molar ratio but increased with increasing aromatic isocyanate (MDI) content in the mixed isocyanate at the constant DMPA content. Tensile strength of the PUD cast films increased and elongation at break decreased with increasing DMPA content at the constant mixed isocyanate molar ratios. In thermal degradation temperature of PUD cast films, the effect of DMPA contents was great but the effect of aromatic isocyanate contents at the low DMPA content was very slight respectively.

• 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 Environmental Science International
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• v.21 no.4
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• pp.507-515
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• 2012

To improve the mechanical properties of hydroxyapatite (HA)/waterborne polyurethane (WBPU) composites, the hydroxyl group of HA was modified by urethane reactions: the hydroxyl groups of HA were reacted with aliphatic or cyclic diisocyanate, and then the modified HAs were extended by adding polyol and/or ${\varepsilon}$-caprolactone. Composites were prepared by the prepolymer process method: the modified HA was directly pured into the urethane reaction of isocyanate and polyol. The properties of modified HA/WBPU composites were investigated by thermogravimetric analysis, tensile strength, and water resistance. The results showed that the reactivity of aliphatic diisocyanate to the hydroxy group of HA was faster than that of cyclic one. Comparing to those of pure HA/WBPU composite films, the thermal stability, water resistance, and mechanical properties of the modified composite films increased with a degree of modification of HA.

• Elastomers and Composites
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• v.58 no.3
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• pp.121-127
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• 2023

The effect of diisocyanate type on the decomposition temperature of polyurethane (PU) hydrolysis was investigated in a subcritical water medium up to 250℃. PU samples were prepared using different types of diisocyanate: two aromatic diisocyanates (4,4'-methylene diphenyl diisocyanate (MDI) and methyl phenylene diisocyanate (TDI)), one unbranched aliphatic diisocyanate (hexamethylene diisocyanate (HDI)), and two cyclic aliphatic diisocyanates (4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI) and isophorone diisocyanate (IPDI)). The pressure had no effect on hydrolysis in the range of 70-250 bar. The decomposition temperature of the PU samples increased in the following order: TDI-PU (199℃) < H₁₂MDI ≈ IPDI ≈ HDI (218-220℃) < MDI-PU (237℃). This order of increase in temperature is related to the electron-donating ability of the group to connected to the nitrogen of the urethane unit. When the temperature of the (PU + water) mixture reached the specific decomposition temperature, the PU samples hydrolyzed completely within 5 min into primary amine and 1,4-butanediol. The hydrolysis products from MDI-PU and H₁₂MDI-PU were separated into a liquid phase rich in (BD + water) and a solid low phase rich in amine, whereas the products from TDI-, IPDI-, and HDI-PU existed in a single aqueous phase.

• Journal of the Korean Applied Science and Technology
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• v.19 no.1
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• pp.25-32
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• 2002

Two PU flame-retardant coatings, 2,3-DBPO/N-l00 (DBPON) and 2,3-DBPO/IL (DBPOI), were prepared by curing 2,3-dibromo modified polyester (2,3-DBPO) with isocyanate curing agent Desmodur N-l00 (or Desmodur IL) at room temperature. The physical properties and flame-retardancy of the two coatings were tested and compared. As a result, the pot-life, yellowness index, lightness index difference, $60^{\circ}$ specular gloss, cross-hatch adhesion, viscosity, and accelerated weathering resistance of DBPON were better than those of DBPOI; the fineness of grind of the two coatings were the same; and the drying time, hardness, and abrasion resistance of DBPOI were better than those of DBPON. The flame retardancy of the flame-retardant coatings increased with the content of the flame retarding component, 2,3-dibromopropanoic acid (2,3-DBP); and the LOI values of the two coatings were in a range of $27{\sim}29%$ when the content of 2,3-DBP was 30wt%.